6202360

Atoms, Molecules
and Lasers
LECTURES PRESENTED AT THE INTERNATIONAL WINTER COLLEGE
TRIESTE
17 JANUARY - 10 APRIL 1973
ORGANIZED BY THE
INTERNATIONAL CENTRE
FOR THEORETICAL PHYSICS,
i m
I N T E R N A T I O N A L A T O M I C ENERGY A G E N C Y , V I E N N A , 1 9 7 4
ATOMS, MOLECULES AND LASERS
Winter College Lectures, Trieste, 1973
CORRIGENDA
Owing to postal difficulties outside the publisher's control, the

following corrections were received after the book had gone to press
RADIOFREQUENCY SPECTROSCOPY, by A. Kastler (pp. 175-211)
Page 177, heading of sub-section 2.3. At the end of the heading add: (Fig. 1)
Page 189, Fig. 15. The ellipses should be replaced by circles
Page 194, Fig. 18. The figure should be as follows:
Y У
X
Page 202, Fig. 24. Delete parts (b) and (c).

HEAVY-PARTICLE COLLISIONS, by R. McCarroIl (pp. 619-677)
Page 622, line above Eq.(1.15). For ( 1.15) read (1.14). 2m

Page 623, Eq. (1.18). Under the equation add: where u = -pp v
n
Page 623, Eq. (1.22). For J ^ read
Page 624, line below Eq. (1.30). For 0 < 0 < 7Г read 0 < в < tj
For if в is read if © is
Page 626, Eq. (1.41). For (tv z) read (t?,z)
Page 621, line 3 after Eq. (1.49). For exp(iq • kz) read exp(iq- kz)
Page 629, Eq. (1.71). The first F on the right-hand side of the equation should be
Page 629, Eq. (1.72) "1
Page 630, first line У For F read
Page 630, Eq. (1.73) J
Page 630, expression between (1.73) and (1.74). For h read h
Page 630, Eq. (1.74). For all h read h
Page 631, statement between Eqs (1.86) and (1.87). For the absolute value of the
average potential is read the absolute value of the average potential, it is
seen from formula (1.84) that
Page 634, caption to Fig. 3. For в read ©
Page 634, Eq. (1.95), The second equality sign should be replaced by a plus sign
Page 638, Eqs (1.111) to (1.114). For b read d
Page 639, Eq. (1.115). For ß(ß+2) read ß(ß+1)
Page 649, first line of sub-section 2.2. For 4 read 1,4
Page 649, Eq. (2.21). For Фр read Ф ь
Page 649, line below Eq. (2.21). For фа read фв
Page 650, end of first line of Eq. (2.25). For v 1 ^ ) read v 2 ^(2)
Page 651, line below Eq. (2.33). For у read m
Page 653, last paragraph of sub-section 2.2, first line. For 1.6 read 1.5
Page 654, first relation displayed. For vt read vt
Page 657, fifth hne from bottom. For intensive read extensive
Page 670, Eq. (3.19). For 2pa u read 2p7Tu'
ATOMS, M O L E C U L E S AND L A S E R S
INTERNATIONAL C E N T R E F O R T H E O R E T I C A L PHYSICS, T R I E S T E
ATOMS, MOLECULES AND LASERS
LECTURES PRESENTED AT
THE INTERNATIONAL WINTER C O L L E G E
A T T R I E S T E F R O M 17 JANUARY TO 10 A P R I L 197 3
ORGANIZED BY THE
INTERNATIONAL C E N T R E F O R T H E O R E T I C A L PHYSICS, T R I E S T E
INTERNATIONAL ATOMIC E N E R G Y AGENCY

VIENNA, 1974
THE INTERNATIONAL C E N T R E F O R T H E O R E T I C A L PHYSICS (ICTP)
in T r i e s t e w a s e s t a b l i s h e d by the I n t e r n a t i o n a l A t o m i c E n e r g y Agency
(IAEA) in 1964 u n d e r an a g r e e m e n t with t h e I t a l i a n G o v e r n m e n t , and with
t h e a s s i s t a n c e of t h e City and U n i v e r s i t y of T r i e s t e .
T h e IAEA and t h e United N a t i o n s E d u c a t i o n a l , S c i e n t i f i c and C u l t u r a l
O r g a n i z a t i o n (UNESCO) s u b s e q u e n t l y a g r e e d to o p e r a t e t h e C e n t r e jointly
f r o m 1 J a n u a r y 1970.
M e m b e r S t a t e s of both o r g a n i z a t i o n s p a r t i c i p a t e in t h e w o r k of t h e C e n t r e ,
t h e m a i n p u r p o s e of which is to f o s t e r , t h r o u g h t r a i n i n g and r e s e a r c h , t h e
a d v a n c e m e n t of t h e o r e t i c a l p h y s i c s , with s p e c i a l r e g a r d to t h e n e e d s of
developing countries.
ATOMS, M O L E C U L E S AND LASERS

IAEA, VIENNA, 1974
STI/PUB/356
ISBN 9 2 - 0 - 1 3 0 3 7 4 - 2
Printed by the IAEA in Austria

D e c e m b e r 1974
FOREWORD
The I n t e r n a t i o n a l C e n t r e f o r T h e o r e t i c a l P h y s i c s h a s m a i n t a i n e d an
i n t e r d i s c i p l i n a r y c h a r a c t e r in i t s r e s e a r c h and t r a i n i n g p r o g r a m m e s in
d i f f e r e n t b r a n c h e s of t h e o r e t i c a l p h y s i c s . In p u r s u a n c e of this o b j e c t i v e ,
the C e n t r e h a s o r g a n i z e d e x t e n d e d r e s e a r c h c o u r s e s with a c o m p r e h e n s i v e
and s y n o p t i c c o v e r a g e in v a r y i n g d i s c i p l i n e s . The f i r s t of t h e s e — on
P l a s m a P h y s i c s — was held in 1964; the s e c o n d , in 1965, was c o n c e r n e d with
the P h y s i c s of P a r t i c l e s . B e t w e e n then and 1972, eight c o u r s e s w e r e
o r g a n i z e d : t h r e e on N u c l e a r T h e o r y (1966, 1969, 1971), t h r e e on the P h y s i c s
of C o n d e n s e d M a t t e r (1967, 1970, 1972), one on C o m p u t i n g as a L a n g u a g e
of P h y s i c s (1971), and one on Global A n a l y s i s and Its A p p l i c a t i o n s (1972).
The p r o c e e d i n g s of all t h e s e c o u r s e s have b e e n p u b l i s h e d by the I n t e r n a -
t i o n a l A t o m i c E n e r g y A g e n c y . The p r e s e n t v o l u m e r e c o r d s the p r o c e e d -
i n g s of the e l e v e n t h c o u r s e , held f r o m 17 J a n u a r y to 10 A p r i l 1973, which
d e a l t with A t o m s , M o l e c u l e s and L a s e r s . G e n e r o u s g r a n t s f r o m the Swedish
I n t e r n a t i o n a l D e v e l o p m e n t A u t h o r i t y and f r o m the N a t h h o r s t F o u n d a t i o n a r e
g r a t e f u l l y a c k n o w l e d g e d . All who attended t h i s c o u r s e will r e m e m b e r the
a m o u n t of w o r k which P r o f e s s o r A. K a s t l e r did u n s e l f i s h l y to e n s u r e i t s
success.
The p r o g r a m m e of l e c t u r e s w a s o r g a n i z e d by P r o f e s s o r s A. K a s t l e r
( F r a n c e ) , B. E d l é n (Sweden), I. K o v á c s (Hungary), and B . L . M o i s e i w i t s c h
(United Kingdom).
Abdus S a l a m
EDITORIAL NOTE
The papers and discussions incorporated in the proceedings published

by the International Atomic Energy Agency are edited by the Agency's edi-
torial staff to the extent considered necessary for the reader's assistance.
The views expressed and the general style adopted remain, however, the
responsibility of the named authors or participants.
For the sake of speed of publication the present Proceedings have been
printed by composition typing and photo-offset lithography. Within the limi-
tations imposed by this method, every effort has been made to maintain a
high editorial standard; in particular, the units and symbols employed are
to the fullest practicable extent those standardized or recommended by the
competent international scientific bodies.
The affiliations of authors are those given at the time of nomination.
The use in these Proceedings of particular designations of countries or
territories does not imply any judgement by the Agency as to the legal status
of such countries or territories, of their authorities and institutions or of
the delimitation of their boundaries.
The mention of specific companies or of their products or brand-names
does not imply any endorsement or recommendation on the part of the
International Atomic Energy Agency.
CONTENTS
P a r t I. ATOMS AND L A S E R S
T h e o r y of a t o m i c s t r u c t u r e and t r a n s i t i o n p r o b a b i l i t i e s
(IAEA-SMR-12/21) 3
S. F e n e u i l l e
T h e o r y of a t o m i c s t r u c t u r e s , t r a n s i t i o n s , and m o l e c u l a r p o t e n t i a l
c u r v e s with e l e c t r o n c o r r e l a t i o n in ground and e x c i t e d s t a t e s
(IAEA-SMR-12/52) 57
0. Sinanoglu
O b s e r v e d s t r u c t u r e of a t o m i c s p e c t r a ( I A E A - S M R - 1 2 / 4 , 5) 93
B. E d l é n
L i n e width and line b r o a d e n i n g ( I A E A - S M R - 1 2 / 1 2 ) 133
W.R. H i n d m a r s h
Radiofrequency spectroscopy (IAEA-SMR-12/9) 175
A. K a s t l e r
N u c l e a r e f f e c t s in a t o m i c s p e c t r a ( I A E A - S M R - 1 2 / 7 ) 213
J. B a u c h e
Highly e x c i t e d a t o m s ( I A E A - S M R - 1 2 / 4 5 ) 241
1.C. Р е г с i v a l
A s t r o p h y s i c a l a p p l i c a t i o n s of a t o m i c p h y s i c s
( I A E A - S M R - 1 2 / 4 4 , 46, 48) 261
M.J. S e a t o n
L a s e r t h e o r y ( I A E A - S M R - 1 2 / 3 2 , 35) 283
H. H a k e n
L a s e r s : e x p e r i m e n t a l and a p p l i c a t i o n s ( I A E A - S M R - 1 2 / 3 1 , 32) 315
D.J. B r a d l e y
P a r t II. MOLECULES
F o u n d a t i o n of the t h e o r y of d i a t o m i c m o l e c u l e s
(IAEA-SMR-12/11) 377
I. К o v á с s
P e r t u r b a t i o n s in the s p e c t r a of d i a t o m i c m o l e c u l e s
(IAEA-SMR-12/42) 411
Hélène L e f e b v r e - B r i o n
Multiplet s t r u c t u r e of s p e c t r a of d i a t o m i c m o l e c u e s
( I A E A - S M R - 1 2 / 3 0 , 37) 449
L.Klynning
P a r t III. COLLISIONS
A t o m i c c o l l i s i o n t h e o r y (IAEA-SMR-12/14) 471
B.L. M o i s e i w i t s c h
A n a l y s i s of e l e c t r o n - a t o m s c a t t e r i n g and p h o t o i o n i z a t i o n
p r o c e s s e s ( I A E A - S M R - 1 2 / 1 7 , 19) 525
P.G. B u r k e
Collisions between electrons'and molecules
( I A E A - S M R - 1 2 / 2 6 , 27) 567
F.H. R e a d
H e a v y - p a r t i c l e c o l l i s i o n ( I A E A - S M R - 1 2 / 4 0 , 41) 619
R. M c C a r r o l l
Photionization (IAEA-SMR-12/50) 679
M. G a v r i l a
F a c u l t y and p a r t i c i p a n t s 703
P A R T I: A T O M S AND L A S E R S
IAEA-SMR-12/21
THEORY O F ATOMIC STRUCTURE

AND TRANSITION P R O B A B I L I T I E S
S. FENEUILLE
Université de Paris-Sud,
Orsay, France
Abstract
THEORY OF ATOMIC STRUCTURE AND TRANSITION PROBABILITIES.

1. G e n e r a l f e a t u r e s of a t o m i c structure theory: 1 . 1 . Introduction; 1 . 2 . Notations and a t o m i c
constants; 1 . 3 . A t o m i c H a m i l t o n i a n s and their s y m m e t r y properties'; 1 . 4 . A p p r o x i m a t i o n methods;
1 . 5 . Conclusion. 2. Elements of group theory: 2 . 1 . F u n d a m e n t a l properties; 2 . 2 . C o n j u g a t e e l e m e n t s -
classes; 2 . 3 . Matrix representations - characters; 2 . 4 . Kronecker product; 2 . 5 . W i g n e r - E c k a r t t h e o r e m .
3. The r o t a t i o n group in t h r e e dimensions: 3 . 1 . I n f i n i t e s i m a l rotations and angular m o m e n t a ; 3 . 2 . Classes
and i r r e d u c i b l e representations; 3 . 3 . Kronecker products - 3j symbols; 3 . 4 . Recoupling c o e f f i c i e n t s - n j symbols.
4 . Tensor operators: 4 . 1 . Definition of i r r e d u c i b l e tensor operators; 4 . 2 . W i g n e r - E c k a r t t h e o r e m ;
4 . 3 . C o u p l e d tensor operators; 4 . 4 . E l e m e n t a r y tensor operators; 4 . 5 . A t o m i c interactions under tensorial
f o r m . 5. Configurations of two e l e c t r o n s : 5 . 1 . L-S coupling; 5 . 2 . j - j coupling; 5 . 3 . Validity of various
couplings; 5 . 4 . Electrons in closed subshells. 6. A n t i s y m m e t r y problems: 6 . 1 . N o n - e q u i v a l e n t electrons;
6 . 2 . Equivalent electrons CPF; 6 . 3 . Second q u a n t i z a t i o n . 7. Static fields: 7 . 1 . U n i f o r m m a g n e t i c f i e l d -
Z e e m a n e f f e c t ; 7 . 2 . Uniform e l e c t r i c f i e l d - Stark e f f e c t ; 8. Field q u a n t i z a t i o n and r a d i a t i v e processes:
8 . 1 . Q u a n t i z e d f r e e e l e c t r o m a g n e t i c f i e l d ; 8 . 2 . G e n e r a l formulas for transition probabilities; 8 . 3 . O n e -
photon r a d i a t i v e processes. 9. E l e c t r i c dipole r a d i a t i v e tiansitions: 9 . 1 . Definitions; 9 . 2 . U n e a n d m u l t i p l e t
f a c t o r s ; 9 . 3 . Transition i n t e g r a l s . 10. Relativistic e f f e c t s in a t o m i c s p e c t r a : 1 0 . 1 . Dirac e q u a t i o n ;
1 0 . 2 . Electron in a c e n t r a l f i e l d ; 1 0 . 3 . Fouldy-Wouthuysen t r a n s f o r m a t i o n ; 1 0 . 4 . Breit i n t e r a c t i o n -
Breit-Pauli approximation.
FOREWORD
To give in f i f t e e n l e c t u r e s a g e n e r a l s u r v e y of the t h e o r y of a t o m i c
s t r u c t u r e and t r a n s i t i o n p r o b a b i l i t i e s is s o m e h o w a t a s k which cannot be
c o m p l e t e l y a c c o m p l i s h e d . F o r t u n a t e l y , t h e r e e x i s t m a n y e x c e l l e n t books
c o v e r i n g the f i e l d ; the m a i n o b j e c t of t h e s e l e c t u r e s was to help the r e a d e r
to u s e t h e m m o r e e a s i l y . Many p a r a g r a p h s a r e t a k e n f r o m v a r i o u s books
and d i f f e r only in d e t a i l f r o m the o r i g i n a l p r e s e n t a t i o n . M o r e o v e r , f o r
s o m e p a r t i c u l a r t o p i c s only r e f e r e n c e s a r e given.
1. G E N E R A L F E A T U R E S O F ATOMIC S T R U C T U R E THEORY
1.1. Introduction
T h e o b j e c t of the t h e o r y of a t o m i c s t r u c t u r e i s the s t u d y of s t a t i o n a r y
s t a t e s of i s o l a t e d a t o m s . At f i r s t s i g h t , t h i s study could a p p e a r to be p u r e l y
a c a d e m i c s i n c e an a t o m is n e v e r t o t a l l y i s o l a t e d and, in any c a s e , m u s t
i n t e r a c t with o t h e r p a r t i c l e s ( e s p e c i a l l y photons) in o r d e r to be o b s e r v e d .
H o w e v e r , in m a n y a t o m i c - p h y s i c s e x p e r i m e n t s (low p r e s s u r e , low photon
d e n s i t y ) the e f f e c t s of a t o m - a t o m and p h o t o n - a t o m i n t e r a c t i o n a r e weak
enough to be n e g l e c t e d , and m o s t of the e x p e r i m e n t a l d a t a c a n be i n t e r -
p r e t e d without t a k i n g t h e m into a c c o u n t .
3
4 FENEUILLE
The s t a t i o n a r y s t a t e s of an a t o m o r , in o t h e r w o r d s , its e n e r g y s p e c t r u m
and the c o r r e s p o n d i n g wave f u n c t i o n s depend on:
(a) the k i n e t i c e n e r g y of the v a r i o u s p a r t i c l e s of the a t o m s , e l e c t r o n s
and n u c l e u s , a n d , t h e r e f o r e , on t h e m a s s of t h e n u c l e u s ,
(b) i n t e r n a l i n t e r a c t i o n s a m o n g which it i s convenient to s e p a r a t e the
n u c l e u s - e l e c t r o n i n t e r a c t i o n and the i n t e r a c t i o n b e t w e e n the e l e c t r o n s . A
p r i o r i , the i n t e r a c t i o n b e t w e e n the n u c l e u s and the e l e c t r o n s d e p e n d s on:
(a) the c h a r g e of the n u c l e u s ,
(b) i t s s t r u c t u r e , i . e . i t s v o l u m e and t h e c h a r g e d i s t r i b u t i o n i n s i d e
this volume,
(c) the r e l a t i v e p o s i t i o n s and v e l o c i t i e s of the n u c l e u s and t h e e l e c t r o n s .
T h e i n t e r a c t i o n b e t w e e n the e l e c t r o n s d e p e n d s on the r e l a t i v e p o s i t i o n s and
v e l o c i t i e s of t h e v a r i o u s e l e c t r o n s .
T h e r e f o r e , in a c o m p l e t e l y g e n e r a l way, t h e p r o b l e m is e x t r e m e l y c o m -
p l i c a t e d and cannot be solved without a p p r o x i m a t i o n s . F i r s t , the n u c l e a r
m a s s i s m u c h l a r g e r t h a n the e l e c t r o n m a s s and t h e n u c l e u s i s m u c h s m a l l e r
t h a n t h e a t o m ; t h e n , in a f i r s t a p p r o x i m a t i o n , it is r e a s o n a b l e to c o n s i d e r
the n u c l e u s to be a point c h a r g e with i n f i n i t e m a s s . T h e n , the i n t e r a c t i o n
b e t w e e n the n u c l e u s and the e l e c t r o n s i s p u r e l y C o u l o m b . M o r e o v e r , the
l a r g e s t p a r t of the i n t e r a c t i o n b e t w e e n the e l e c t r o n s i s t h e e l e c t r o s t a t i c
C o u l o m b t e r m and one can e x p e c t that the r e l a t i v e v e l o c i t i e s of e l e c t r o n s
in a t o m s a r e s m a l l enough to be n e g l e c t e d . In f a c t , to r e p r o d u c e i m p o r t a n t
e x p e r i m e n t a l f e a t u r e s , it is n e c e s s a r y to i n t r o d u c e a m a g n e t i c t e r m : t h e
w e l l - k n o w n s p i n - o r b i t i n t e r a c t i o n . As r e g a r d s the r e m a i n i n g e f f e c t s , one
a s s u m e s in g e n e r a l t h a t t h e y a r e s m a l l enough to be i n t r o d u c e d by m e a n s
of p e r t u r b a t i o n t h e o r y . T h e y a r e , e s s e n t i a l l y , r e l a t i v i s t i c c o r r e c t i o n s and
h y p e r f i n e n u c l e a r e f f e c t s ( h y p e r f i n e s t r u c t u r e and i s o t o p e s h i f t ) . The n u c l e a r
e f f e c t s in a t o m i c s p e c t r a will be studied in a n o t h e r p a p e r and, t h e r e f o r e ,
we s h a l l not c o n s i d e r t h e m in t h i s p a p e r . The r e l a t i v i s t i c e f f e c t s , . o n the
o t h e r hand, will be i n v e s t i g a t e d only in a n o n - s o p h i s t i c a t e d way, e x c l u d i n g
quantum electrodynamics.
1.2. N o t a t i o n s and a t o m i c c o n s t a n t s
To avoid r e p e a t i n g m a n y t i m e s the n o t a t i o n s to be u s e d and to give

i m m e d i a t e l y the o r d e r of m a g n i t u d e of a t o m i c q u a n t i t i e s , we s h a l l i n t r o d u c e
t h e m r i g h t away:
ц ( m a s s of e l e c t r o n ) = 9.109 X 10" 2 8 g
-e ( c h a r g e of e l e c t r o n ) = 4.770 X 10" 10 e s u
ft (quantum c o n s t a n t ) = h/2-п = 1.055 X 10" 27 g - c m 2 - s _ 1
с (light v e l o c i t y ) = 2.99792 X 10 1 0 c m • s
a0 (Bohr r a d i u s ) = й 2 / й е 2 = 0.5292 X 10 _ 8 c m
a (fine s t r u c t u r e c o n s t a n t ) = e 2 / c f t = 1 / 1 3 7 . 0 3 6 0 8
R ( R y d b e r g c o n s t a n t ) = a 2 ß c 2 / 2 h c = 109737.31 c m " 1
ß (Bohr m a g n e t o n ) = e f t / 2 ^ c = 0.9274 X 10" 2 0 e r g • G _ 1 .
1.3. A t o m i c H a m i l t o n i a n s and t h e i r s y m m e t r y p r o p e r t i e s
If we u s e t h e a p p r o x i m a t i o n s defined in s u b s e c t i o n 1.1, the n o n - r e l a t i v i s t i c

H a m i l t o n i a n can be w r i t t e n a s
IAEA-SMR-12 / 2 1 5
i i> j
H e r e , Pj i s the l i n e a r m o m e n t u m of the e l e c t r o n i, r j i s the d i s t a n c e
b e t w e e n t h i s e l e c t r o n and the n u c l e u s situated at t h e o r i g i n of c o - o r d i n a t e s ,
r j j i s the d i s t a n c e b e t w e e n the e l e c t r o n s i and j, Ze i s the n u c l e a r c h a r g e ,
and the s u m s r u n o v e r the e l e c t r o n s .
F i r s t , it i s c l e a r t h a t H i s i n v a r i a n t u n d e r i n v e r s i o n with r e s p e c t to the
o r i g i n . T h e r e f o r e , t h e e i g e n s t a t e s of H NR have w e l l - d e f i n e d p a r i t y ; in o t h e r
w o r d s , p a r i t y i s a good q u a n t u m n u m b e r f o r a t o m i c s t a t e s .
Now, if we d e f i n e the t o t a l o r b i t a l a n g u l a r m o m e n t u m L (without
d i m e n s i o n ) by:
L = (l/fi){?i Xpi}
i
it i s e a s y to show t h a t
[HNR,£]=O .
s i n c e f o r any v a l u e of i and j:
[í*i,(Pj) 2 ] = 0
1 1 1
(let u s r e c a l l that Vj — = , V; — = - V, — = ). T h u s , (E,)2 and L z
r r r r r
i i ij ij ij
which c o m m u t e a r e c o m p a t i b l e i n v a r i a n t s f o r H NR and the e i g e n s t a t e s of
H NR c a n be a l s o e i g e n s t a t e s of t h e s e o p e r a t o r s ; the c o r r e s p o n d i n g e i g e n -
v a l u e s L ( L + 1) (in f a c t , one u s e s g e n e r a l l y L) and M L can be u s e d f o r
l a b e l l i n g the e i g e n f u n c t i o n s of H NR .
F u r t h e r m o r e , H ^ r d o e s not depend on spin v a r i a b l e s , and, t h e r e f o r e ,
the t o t a l spin S = ^ s, c o m m u t e s with H N R . T h u s , the e i g e n v a l u e s of (S)
i
(S(S + 1), but one u s e s g e n e r a l l y S) and S z (M s ) c a n be u s e d f o r l a b e l l i n g
the e i g e n s t a t e s of H NR .
F i n a l l y , the e i g e n s t a t e s of H NR can be w r i t t e n a s
P SMSLML>
w h e r e y c o n t a i n s a l l t h e i n f o r m a t i o n r e q u i r e d to d e f i n e s t a t e s u n a m b i g o u s l y
and p i s the p a r i t y n u m b e r e q u a l to + 1 (even s t a t e s ) o r - 1 (odd s t a t e s ) .
H o w e v e r , we have a l r e a d y noticed that, in o r d e r to r e p r o d u c e i m p o r t a n t
e x p e r i m e n t a l f e a t u r e s , it i s n e c e s s a r y to i n t r o d u c e s p i n - o r b i t i n t e r a c t i o n .
The c o r r e s p o n d i n g m a g n e t i c (or r e l a t i v i s t i c ) t e r m c a n be w r i t t e n a s
= J i )
'
6 FENEUILLE
a s we s h a l l s e e when we study r e l a t i v i s t i c e f f e c t s in d e t a i l . It is c l e a r t h a t
n e i t h e r П nor S c o m m u t e with V s o , s i n c e the t h r e e c o m p o n e n t s of (or Sj )
do not c o m m u t e with one a n o t h e r . T h e r e f o r e , f o r the e i g e n s t a t e s of H d e f i n e d
by
H = HNR+ v s o
S, M s , L , M L a r e no l o n g e r good q u a n t u m n u m b e r s . Now, if we d e f i n e the

t o t a l a n g u l a r m o m e n t u m J by J = S + L , we can show e a s i l y that i t s t h r e e
c o m p o n e n t s c o m m u t e with H. T h u s , the e i g e n s t a t e s of H can be l a b e l l e d
by the e i g e n v a l u e s of (J) 2 and J z and they can be w r i t t e n a s
I TP J M J >
s i n c e it i s o b v i o u s t h a t H i s s t i l l p a r i t y i n v a r i a n t . T h e s e i n v a r i a n c e p r o p e r -
t i e s a r e valid f o r any a t o m i c H a m i l t o n i a n , even f u l l y r e l a t i v i s t i c , a s long
a s the t o t a l a n g u l a r m o m e n t u m Ï of the n u c l e u s i s z e r o . If not, only
( F ) 2 = (! + J ) 2 and F z =I Z + J z c o m m u t e with t h e a t o m i c H a m i l t o n i a n ; in t h i s
c a s e , J and M j a r e no l o n g e r good q u a n t u m n u m b e r s . H o w e v e r ; n u c l e a r
p e r t u r b a t i o n is in g e n e r a l e x t r e m e l y s m a l l and u n d e r t h e s e c o n d i t i o n s ,
J and M j can s t i l l be c o n s i d e r e d as good q u a n t u m n u m b e r s . In t h e s a m e
way, t h e s p i n - o r b i t e n e r g y i s v e r y o f t e n r a t h e r s m a l l c o m p a r e d with the
d i s t a n c e s b e t w e e n n o n - r e l a t i v i s t i c e n e r g y l e v e l s ; t h e n , S and L r e m a i n
a p p r o x i m a t e q u a n t u m n u m b e r s and can be u s e d , but only a s an a p p r o x i m a t i o n ,
to l a b e l the e i g e n s t a t e s of H which r e a d in t h i s c a s e
ITPSLJMJ)
H o w e v e r , in m a n y c a s e s t h i s a p p r o x i m a t i o n i s not valid a s , e . g . f o r noble

g a s s p e c t r a w h e r e , a s we s h a l l s e e l a t e r , it i s p o s s i b l e to define o t h e r
a p p r o x i m a t e q u a n t u m n u m b e r s in o r d e r to l a b e l t h e s t a t e s .
1.4. A p p r o x i m a t i o n m e t h o d s
T h e p h y s i c a l a p p r o x i m a t i o n s defined in s u b s e c t i o n 1.1 a r e i n s u f f i c i e n t
to s o l v e (i.e. to d e t e r m i n e the e i g e n v a l u e s and e i g e n f u n c t i o n s ) the S c h r ö d i n g e r
equation f o r m a n y - e l e c t r o n a t o m s even in the n o n - r e l a t i v i s t i c c a s e . T h e r e -
f o r e , one of the m o s t i m p o r t a n t a c t i v i t i e s in the t h e o r y of a t o m i c s t r u c t u r e
w a s (and s t i l l i s ) to find m a t h e m a t i c a l a p p r o x i m a t i o n s ( s o m e t i m e s on a
p h y s i c a l b a s i s ) which allow u s to obtain a p p r o x i m a t e s o l u t i o n s to t h e a t o m i c
p r o b l e m . M o s t of t h e s e s t a r t with an i n d e p e n d e n t - p a r t i c l e m o d e l ; in t h i s
c h a p t e r we s h a l l study only the v a r i o u s ways of u s i n g s u c h a m o d e l and we
s h a l l exclude m o r e s o p h i s t i c a t e d t r e a t m e n t s , such a s c o n f i g u r a t i o n i n t e r -
actions or correlation effects.
1.4.1. C e n t r a l field a p p r o x i m a t i o n
The p r i n c i p l e of t h i s a p p r o x i m a t i o n i s v e r y s i m p l e : one t r i e s to
d e t e r m i n e a c e n t r a l p o t e n t i a l U ( r ) , whose e f f e c t s a r e c l o s e enough to t h o s e
of C o u l o m b i n t e r a c t i o n b e t w e e n all the p a r t i c l e s of t h e a t o m to p e r m i t a
c a l c u l a t i o n of r e s i d u a l i n t e r a c t i o n s by m e a n s of p e r t u r b a t i o n t h e o r y .
M a t h e m a t i c a l l y , t h i s m e a n s that we split the a t o m i c H a m i l t o n i a n into two
p a r t s of quite d i f f e r e n t o r d e r s of m a g n i t u d e :
IAEA-SMR-12 / 2 1 7
H = н0 +н1
Ho = ^ (Pj) 2 - e U ( r j )j- (principal Hamiltonian)
Ze2} e2
+ eU(r. ) - — — r + ) ~ + Vs0 (perturbing Hamiltonian)
1J
i i>j
The wave f u n c t i o n s and the e i g e n v a l u e s of Ho c a n be obtained e a s i l y s i n c e
a l l the c o - o r d i n a t e s can be s e p a r a t e d . We r e c a l l t h a t , f o r bound s t a t e s ,
the e i g e n v a l u e s of h, d e f i n e d by
h (p)2-eU(r)
a r e l a b e l l e d by the two q u a n t u m n u m b e r s n and Í ( i < n , i n t e g e r s ) while

the c o r r e s p o n d i n g wave f u n c t i o n s depend on the f i v e q u a n t u m n u m b e r s n , s ,
m s , I , nijf (or n , s , I , j, m j ) . M o r e p r e c i s e l y
h | n s m s i m , ) = e n{ | n s m s Í m {)>
I n s m s \ i т { >
|üm { ]> = Y í r r ] í (6,9), ( s p h e r i c a l h a r m o n i c ) , | s m s ) > (spin f u n c t i o n )
d2 1(1 + 1) 2M
d r 2 ní r 2 ^ni"1" f j 2 t c
n{
F o r a C o u l o m b a t t r a c t i v e p o t e n t i a l U(r) = Z e / r ,
-Z2
e e q 2 c 2
ni = n = 2^2 ^
In any c a s e , ( n - i - 1 ) is t h e n u m b e r of n o d e s of R n i ( r ) excluding o r i g i n and

infinity.
E n e r g y l e v e l s of Ho. The d i s c r e t e e i g e n v a l u e s of H 0 can be w r i t t e n

as follows:
E 0 = ^ N(ni) e n t , ^ N ( n i ) = N ( n u m b e r of e l e c t r o n s )
ne ní
N(ní) b e i n g the n u m b e r of e l e c t r o n s in the s u b s h e l l ni. The P a u l i e x c l u s i o n
p r i n c i p l e i m p l i e s a s u p p l e m e n t a r y condition
N(nje) S (4Í +2)
Giving the n u m b e r s N(ni) i s e q u i v a l e n t to d e f i n i n g an e l e c t r o n c o n f i g u r a t i o n

which r e a d s
, 0 Мщк) , . .ВДМг)
(n x ii) (n2i2)
with a single e n e r g y l e v e l in z e r o - o r d e r a p p r o x i m a t i o n .
8 FENEUILLE
F o r n e u t r a l a t o m s , the g r o u n d c o n f i g u r a t i o n , i . e . t h a t of l o w e s t e n e r g y ,
i s g i v e n b y M a d e l u n g 1 s e m p i r i c a l r u l e w h i c h d e r i v e s f r o m a n a n a l y s i s of M e n d e l e e v ' s
t a b l e ; it c a n b e f o r m u l a t e d a s f o l l o w s : the e n e r g y of a o n e - e l e c t r o n o r b i t
i n c r e a s e s w i t h (n + i ) and if (n + i ) i s f i x e d , it g r o w s a s n i s g r o w i n g . T h u s
eis < e2s < e 2p< e 3s < e 3 p < e 4s < e 3 d - " • F o r h i g h l y i o n i z e d a t o m s , which a r e
n e a r l y h y d r o g e n i c , t h e a b o v e r u l e is not v a l i d and we s e e t h a t e n i i n c r e a s e s
with i n c r e a s i n g n a n d , f o r f i x e d n , with SL. T h e n , in p a r t i c u l a r , e 3 d < e 4 s .
T h e d i s c r e t e s p e c t r u m of l i g h t a t o m s c a n be u s u a l l y d e s c r i b e d by
o n e - e l e c t r o n e x c i t a t i o n s f r o m t h e h i g h e s t - e n e r g y s u b s h e l l of the g r o u n d
c o n f i g u r a t i o n . F o r e x a m p l e , the ground c o n f i g u r a t i o n of n e u t r a l s o d i u m
(Na I) i s I s 2 2 s 2 2p6 3 s and a l l t h e d i s c r e t e l e v e l s of t h e c o r r e s p o n d i n g
s p e c t r u m b e l o n g t o t h e c o n f i g u r a t i o n s I s 2 2 s 2 2 p 6 n i . We m u s t m e n t i o n
t h a t , f o r h i g h v a l u e s of n , the e n e r g i e s of t h e s e c o n f i g u r a t i o n s h a v e the
s a m e l i m i t , n a m e l y , the g r o u n d - s t a t e e n e r g y of Na + ; t h e r e f o r e , t h e r e a p p e a r
s o m e s t r u c t u r e s w h i c h a r e s i m i l a r to t h o s e e n c o u n t e r e d in t h e h y d r o g e n
s p e c t r u m and w h i c h a r e c a l l e d R y d b e r g s e r i e s . F o r h e a v i e r a t o m s , t h e
e n e r g y s e p a r a t i o n b e t w e e n t h e o u t e r m o s t s u b s h e l l b e c o m e s v e r y s m a l l with
r e s p e c t t o r e s i d u a l i n t e r a c t i o n s and s o m e d i s c r e t e l e v e l s o b s e r v e d b e l o n g
to configurations r e s u l t i n g f r o m t w o - e l e c t r o n excitations (configuration
4p 3d of C a I, f o r e x a m p l e ) . T h i s is a l w a y s t h e c a s e f o r t r a n s i t i o n e l e m e n t s ,
r a r e e a r t h s and a c t i n i d e s e s p e c i a l l y . On t h e o t h e r h a n d , t h e r e a r e m a n y
c o n f i g u r a t i o n s w h o s e e n e r g i e s a r e v e r y c l o s e to the g r o u n d e n e r g y and s o m e -
t i m e s M a d e l u n g ' s r u l e d o e s not apply a n y l o n g e r . F o r e x a m p l e , in n e u t r a l
r a r e e a r t h s p e c t r a , we o b s e r v e m a n y e n e r g y l e v e l s v e r y c l o s e to one a n o t h e r
which b e l o n g to t h e c o n f i g u r a t i o n s S s 2 4 f n , 6s 4 f n 5d, 6 s 2 4 f n " 1 6 p , and
6s 4f n " 1 5d 6p, r e s p e c t i v e l y . It i s obvious t h a t , in t h i s c a s e , the c o r r e s p o n d i n g
l i n e s p e c t r a h a v e no s i m p l e s t r u c t u r e s and u s u a l l y t h e r e a r e a l a r g e n u m b e r
of l i n e s i n s i d e a n a r r o w s p e c t r a l r a n g e : t h e s e a r e c o m p l e x s p e c t r a .
B e y o n d d i s c r e t e s t a t e s with e n e r g i e s l o w e r t h a n t h a t of t h e f i r s t
i o n i z a t i o n l e v e l , t h e r e a r e a c o n t i n u u m and d i s c r e t e s t a t e s with e n e r g i e s
higher than the f o r m e r s . T h e s e d i s c r e t e s t a t e s a r e auto-ionizing s t a t e s
s i n c e u s u a l l y , when a n a t o m i s in s u c h a s t a t e , i t l o s e s a n e l e c t r o n s p o n -
t a n e o u s l y . T h e o b s e r v e d a u t o - i o n i z i n g s t a t e s a r e u s u a l l y d u e to o n e - e l e c t r o n
e x c i t a t i o n of a l o w - l y i n g c o m p l e t e s u b s h e l l o r to t w o - e l e c t r o n e x c i t a t i o n
( I s 2 s 2 and I s 2p 2 of L i I, f o r e x a m p l e ) . We m u s t n o t e t h a t the l i n e s o b s e r v e d
i n X - r a y e m i s s i o n s p e c t r a a r e d u e t o t r a n s i t i o n s b e t w e e n l e v e l s of t h i s t y p e .
W a v e f u n c t i o n s of Hq_. In g e n e r a l , t h e e l e c t r o n c o n f i g u r a t i o n i s h i g h l y
d e g e n e r a t e . T h i s m e a n s t h a t i t can be d e s c r i b e d b y a l a r g e n u m b e r of
d i f f e r e n t q u a n t u m s t a t e s . T h e s e s t a t e s c a n be d e f i n e d by g i v i n g N a t o m i c
o r b i t s (an o r b i t b e i n g d e f i n e d b y ф = n s m s Î m^ ) and b y t a k i n g into a c c o u n t
P a u l i ' s a n t i s y m m e t r y p r i n c i p l e ; such a s t a t e c a n be r e p r e s e n t e d by a
Slater determinant
•Ml) <M 1)
{<í>i 0s «М -
•MS) <ys)
Фгт * (N)
S u b s c r i p t s l a b e l o r b i t s ; i n d i c e s within p a r e n t h e s e s l a b e l e l e c t r o n s . It i s
e a s y to s h o w t h a t t h e n u m b e r of d i s c r e t e s t a t e s c o r r e s p o n d i n g to the c o n -
figuration ( П ! ^ ) ^ " ! ^ (n2í2)N(nzt2) is equal to
IAEA-SMR-12 / 2 1 9
q_ g!
where С
P~ P'(Q-P)!
F o r e x a m p l e , the c o n f i g u r a t i o n I s 2 2s 2 2p 2 3s c o n t a i n s c f X c f X CÍj X С 2 = 30
discrete states.
H o w e v e r , in o r d e r to t a k e into account r e s i d u a l i n t e r a c t i o n s , we have
to d i a g o n a l i z e the m a t r i x of H 1 f o r the s t a t e s of the c o n f i g u r a t i o n c o n s i d e r e d ;
t h i s p r o b l e m can be l a r g e l y s i m p l i f i e d if we can u s e the s y m m e t r y p r o p e r t i e s
of the H a m i l t o n i a n . We know that in p a r t i c u l a r the m a t r i x of H 1 i s d i a g o n a l
with r e s p e c t to J and i n d e p e n d e n t of Mj b e c a u s e of s p h e r i c a l s y m m e t r y .
M o r e o v e r , t h e m a t r i x of t h e m o s t i m p o r t a n t p a r t of H 1 , i . e . the e l e c t r o -
s t a t i c p a r t , i s d i a g o n a l with r e s p e c t to S and L . U n f o r t u n a t e l y , S l a t e r d e t e r -
m i n a n t s a r e u s u a l l y not e i g e n f u n c t i o n s of S 2 , L 2 and J 2 ; only M s , M L and
Mj a r e well d e f i n e d . One p o s s i b l e way of s o l v i n g t h i s p r o b l e m is to u s e
s u c h l i n e a r c o m b i n a t i o n s of S l a t e r d e t e r m i n a n t s which a r e e i g e n f u n c t i o n s
of S 2 , L 2 and J 2 . H o w e v e r , though p o s s i b l e in p r i n c i p l e , t h i s m e t h o d b e c o m e s
e x t r e m e l y t e d i o u s , e s p e c i a l l y when t h e r e a r e s e v e r a l e q u i v a l e n t o r b i t s in
t h e c o n f i g u r a t i o n s t u d i e d . F o r t u n a t e l y , it i s p o s s i b l e c o m p l e t e l y to avoid
t h e c o n s t r u c t i o n of s u c h c o m b i n a t i o n s of S l a t e r d e t e r m i n a n t s by u s i n g a n g u l a r -
m o m e n t u m a l g e b r a and by d e f i n i n g the s t a t e s a s r e s u l t i n g f r o m a coupling
of the v a r i o u s individual a n g u l a r m o m e n t a . The r u l e s f o r coupling of two
d i s t i n c t a n g u l a r m o m e n t a a r e v e r y s i m p l e , but f o r e q u i v a l e n t o r b i t s the
p r o b l e m b e c o m e s m o r e c o m p l e x , s i n c e we have to t a k e into a c c o u n t the
a n t i s y m m e t r y p r i n c i p l e . An i m p o r t a n t p a r t of t h i s p a p e r will be devoted
to s t u d y i n g a n g u l a r - m o m e n t u m a l g e b r a t e c h n i q u e s and m e t h o d s allowing the
b u i l d - u p of w e l l - d e f i n e d s t a t e s f o r e q u i v a l e n t e l e c t r o n c o n f i g u r a t i o n s .
The e n e r g y m a t r i x . In a f i r s t a p p r o x i m a t i o n , the e n e r g y l e v e l s belonging

to a given c o n f i g u r a t i o n a r e obtained by d i a g o n a l i z i n g the m a t r i x of H j f o r
t h e s t a t e s of t h i s c o n f i g u r a t i o n . Such a d i a g o n a l i z a t i o n can be avoided if
V s 0 i s negligible with r e s p e c t to C o u l o m b i n t e r a c t i o n and if t h e r e i s only
one t e r m (SL) of a given type; g e n e r a l l y , h o w e v e r , in o r d e r to obtain a c c u r a t e
wave f u n c t i o n s , it i s n e c e s s a r y to p e r f o r m t h i s d i a g o n a l i z a t i o n . In any c a s e ,
we have to e v a l u a t e t h e m a t r i x e l e m e n t s of H j . T h e s e m a t r i x e l e m e n t s can
a l w a y s be w r i t t e n as a f i n i t e s u m of t e r m s which c o n s i s t s of a r a d i a l p a r t
and an a n g u l a r p a r t . The a n g u l a r p a r t can be c a l c u l a t e d without d i f f i c u l t y
by u s i n g a n g u l a r - m o m e n t u m a l g e b r a , but c o m p u t a t i o n of the r a d i a l p a r t
r e q u i r e s the knowledge of U ( r ) . We s h a l l not d i s c u s s t h i s p r o b l e m in d e t a i l
b u t , in f a c t , it i s s o m e t i m e s p o s s i b l e to avoid it by c o n s i d e r i n g the r a d i a l
p a r t s of the m a t r i x e l e m e n t s a s p a r a m e t e r s to be f i t t e d to e x p e r i m e n t a l
data. This s e m i - e m p i r i c a l method is p a r t i c u l a r l y useful f o r analysing
complex spectra.
If we a r e i n t e r e s t e d in obtaining a c c u r a t e r a d i a l wave f u n c t i o n s , and
if coupling i s n e a r l y p u r e (i.e. if we can avoid any d i a g o n a l i z a t i o n of H j ,
i . e . if we can n e g l e c t s p i n - o r b i t i n t e r a c t i o n ) , a convenient way i s to u s e
the v a r i a t i o n p r i n c i p l e and the s o - c a l l e d H a r t r e e - F o c k a p p r o x i m a t i o n which
we a r e going to d i s c u s s b r i e f l y in the next s e c t i o n .
1.4.2. Hartree-Fock approximation
The key idea of t h i s type of a p p r o x i m a t i o n is b a s e d on the f a c t that the

S c h r ö d i n g e r equation i s t h e d i f f e r e n t i a l equation c o r r e s p o n d i n g to a m i n i m u m
10 FENEUILLE
p r o b l e m in v a r i a t i o n a l c a l c u l u s . In f a c t , it i s e a s y to show t h a t •( ф
i s s t a t i o n a r y f o r |i/<)> in the neighbourhood of e a c h of the n o r m a l i z e d e i g e n -
f u n c t i o n s of H and that the s t a t i o n a r y v a l u e i s equal to the c o r r e s p o n d i n g
allowed v a l u e . T h e r e f o r e , i n s t e a d of s e e k i n g throug'h i t s S c h r ö d i n g e r
e q u a t i o n , one c a n t r y to r e p r e s e n t the unknown f u n c t i o n \фУ a s belonging
to a c l a s s of f u n c t i o n s and to apply the v a r i a t i o n a l p r i n c i p l e to t h i s c l a s s
of f u n c t i o n s . O b v i o u s l y , f o r h e a v y a t o m s with m a n y e l e c t r o n s , t h i s c l a s s
cannot be unbounded and, t h e r e f o r e , the m e t h o d y i e l d s only t h a t m e m b e r of
the f a m i l y which g i v e s the c l o s e s t f i t to t h e t r u e e i g e n f u n c t i o n and it i s only
an a p p r o x i m a t i o n . T h i s a p p r o x i m a t i o n d e p e n d s on the type of t r i a l f u n c t i o n
a d m i t t e d f o r |i//)>. The m o s t f a m o u s t r i a l f u n c t i o n and c e r t a i n l y t h e e a s i e s t
to w o r k with i s t h e H a r t r e e - P o c k f u n c t i o n .
F r o m c e n t r a l f i e l d a p p r o x i m a t i o n we know t h a t , in an i n d e p e n d e n t -
p a r t i c l e m o d e l , one can r e p r e s e n t an a t o m i c s t a t e by a S l a t e r d e t e r m i n a n t
b u i l t up f r o m a t o m i c o r b i t s of the type:
| n s i m s m i ) = -i R n i (r ) | s m s У | i m цУ
The H a r t r e e - P o c k f u n c t i o n is of the s a m e type and t h e r e f o r e only the r a d i a l

f u n c t i o n s R n j / r a r e s u b j e c t to v a r i a t i o n , but they a r e not s p e c i f i e d to be
s o l u t i o n s of a p a r t i c u l a r c e n t r a l field p r o b l e m . E s p e c i a l l y , the R n i ( r )
f u n c t i o n s depend on the p a r t i c u l a r c o n f i g u r a t i o n being c o n s i d e r e d a n d , a s a
c o n s e q u e n c e , the R n i ( r ) f u n c t i o n s obtained f o r the d i f f e r e n t c o n f i g u r a t i o n s
a r e not o r t h o g o n a l and, t h u s , cannot be m a d e the b a s i s f o r a c a l c u l a t i o n in
which c o n f i g u r a t i o n i n t e r a c t i o n i s t a k e n into a c c o u n t by p e r t u r b a t i o n t h e o r y .
H o w e v e r , it i s p o s s i b l e to i n t r o d u c e c o n f i g u r a t i o n i n t e r a c t i o n by u s i n g the
v a r i a t i o n a l p r i n c i p l e only. A s r e g a r d s the H a r t r e e - P o c k e q u a t i o n s , t h e y
will not be d i s c u s s e d in d e t a i l in a n o t h e r c h a p t e r , s i n c e we plan to d e s c r i b e
e s s e n t i a l l y the m e t h o d s allowing us to c a l c u l a t e the a n g u l a r p a r t of t h e
m a t r i x e l e m e n t s of H j .
1.4.3. L a y z e r expansion
If we change r into p = r Z , p b e c o m e s Ťr = ( l / Z ) p and t h e r e f o r e the n o n -

r e l a t i v i s t i c H a m i l t o n i a n t a k e s the f o r m
^[Zfe^-ÍKXÍ]
i i> j
a n d , if Z i s l a r g e , we can w r i t e , a c c o r d i n g to p e r t u r b a t i o n t h e o r y ,
E = Z 2 ( A 0 + A j Z " 1 + A 2 Z " 2 + ...)
Since t h e u n p e r t u r b e d H a m i l t o n i a n i s p u r e l y hydro g e n i e , A 0 d e p e n d s only
on the n u m b e r of e l e c t r o n s N(n) in e a c h s h e l l n. M o r e p r e c i s e l y
A0 = ^ N ( n ) { - « 2 M C 2 ^ }
To give the n u m b e r N(n) i s e q u i v a l e n t to t h e d e f i n i t i o n of a c o m p l e x

e x p r e s s i o n which r e a d s n ^ ^ n ^ " 2 ' ... , with a single e n e r g y l e v e l in z e r o -
order approximation.
IAEA-SMR-12 / 2 1 11
O b v i o u s l y , a c o m p l e x i s highly d e g e n e r a t e , s i n c e g e n e r a l l y it c o n t a i n s
m a n y c o n f i g u r a t i o n s and in o r d e r to obtain Aj^ we have to d i a g o n a l i z e t h e
m a t r i x of
i>j
f o r the s t a t e s of t h e c o n s i d e r e d c o m p l e x . C o n s e q u e n t l y , t h i s m e t h o d s e e m s
to be m o r e c o m p l i c a t e d than the u s u a l c e n t r a l f i e l d t h e o r y . H o w e v e r , it i s
p a r t i c u l a r l y well suited to study i s o e l e c t r o n i c s e q u e n c e s (since l / Z i s the
e x p a n s i o n p a r a m e t e r ) and s i n c e we w o r k with h y d r o g e n i c wave f u n c t i o n s ,
a l l t h e f o r m u l a s can be w r i t t e n in an a n a l y t i c a l f o r m . F o r n e u t r a l a t o m s ,
n e v e r t h e l e s s , the f i r s t two t e r m s p r o v i d e but a r a t h e r p o o r a p p r o x i m a t i o n
(which i s o b v i o u s f r o m M a d e l u n g ' s r u l e ) and t h e r e f o r e , s i n c e i s o e l e c t r o n i c
s e q u e n c e s will be studied in a n o t h e r p a p e r , we s h a l l not d e s c r i b e the L a y z e r
e x p a n s i o n in g r e a t e r d e t a i l .
1.5. C o n c l u s i o n and c o n t e n t s of the p a p e r
The m a i n p r o b l e m in the t h e o r y of a t o m i c s t r u c t u r e is to c a l c u l a t e the

m a t r i x e l e m e n t s . We have s e e n t h a t , in i n d e p e n d e n t - p a r t i c l e m o d e l s , t h e s e
m a t r i x e l e m e n t s can be s e p a r a t e d into a r a d i a l and an a n g u l a r p a r t . F i r s t ,
we s h a l l d e s c r i b e the g e n e r a l m e t h o d s allowing u s to obtain the a n g u l a r
p a r t , with s p e c i a l r e f e r e n c e to s y m m e t r y p r o p e r t i e s . T h e r e f o r e , we s h a l l
r e c a l l f i r s t the f u n d a m e n t a l p o i n t s of g r o u p t h e o r y , t h e n we s h a l l study
a n g u l a r m o m e n t u m a l g e b r a and t h e c o n c e p t of f r a c t i o n a l p a r e n t a g e which
i s e s s e n t i a l f o r the s t u d y of e q u i v a l e n t e l e c t r o n c o n f i g u r a t i o n s . C o n f i g u r a t i o n
i n t e r a c t i o n will be studied in a s e c o n d a p p r o x i m a t i o n by u s i n g second
q u a n t i z a t i o n t e c h n i q u e s . A f t e r w a r d s , the m o s t i m p o r t a n t f e a t u r e s a p p e a r i n g
in the c a l c u l a t i o n of t r a n s i t i o n p r o b a b i l i t i e s will be studied with s p e c i a l
r e f e r e n c e to i n t e r m e d i a t e coupling and c o n f i g u r a t i o n e f f e c t s and, f i n a l l y ,
the f u n d a m e n t a l a s p e c t s of r e l a t i v i s t i c t h e o r y will be d e s c r i b e d in an
elementary form.
2. E L E M E N T S OF GROUP THEORY
2.1. F u n d a m e n t a l p r o p e r t i e s
2.1.1. Group
A g r o u p i s a s e t (finite o r infinite) of e l e m e n t s R j ... R g ... which

s a t i s f y the following conditions:
(a) e v e r y p a i r of e l e m e n t s R Q , R p can be c o m b i n e d to a p r o d u c t R 0 R
which a l s o b e l o n g s to the s e t ;
(b) t h i s p r o d u c t i s a s s o c i a t i v e : R T ( R 0 R ) = ( R T R 0 ) R p ;
(c) the s e t c o n t a i n s an i d e n t i t y e l e m e n t I s u c h t h a t R 0 I = I R 0 = R 0 ;
(d) f o r e a c h e l e m e n t R 0 t h e r e e x i s t s an i n v e r s e e l e m e n t R - i belonging
to the s e t , i . e . R p R ; 1 = R ^ R , , = I.
12 FENEUILLE
2.1.2. Subgroup
If it i s p o s s i b l e to find a m o n g the e l e m e n t s of a g r o u p G a s u b s e t which

i s a g r o u p H, then H i s a s u b g r o u p of G, that i s
GDH
2.1.3. Direct product
If t h e e l e m e n t s of two g r o u p s G f R j R g ...) and G ' i R ' j R ^ ...) c o m m u t e

[R0RV = R ' T R 0 ] , t h e n the s e t of e l e m e n t s R v R 2 R ' j , R' 2 . . . , (R R' T ), ...
i s a g r o u p ; t h i s g r o u p i s the d i r e c t p r o d u c t of the two g r o u p s G and G 1 .
It r e a d s GXG'.
2.1.4. I s o m o r p h i s m and h o m o m o r p h i s m
Two g r o u p s G and H a r e said to be i s o m o r p h i c if a unique c o r r e s p o n d e n c e

can be d r a w n b e t w e e n the e l e m e n t s RJR2 ... of G and Р Х Р 2 ... of H s u c h
that
R 0 R p = RT if P 0 P p = PT
If the c o r r e s p o n d e n c e i s not unique, and if one and only one e l e m e n t

of G c o r r e s p o n d s to any a r b i t r a r y e l e m e n t of H, then H i s h o m o m o r p h i c
to G.
2.2. C o n j u g a t e e l e m e n t s — c l a s s e s
The e l e m e n t R T = R p R 0 R" p 1 i s said t o ' b e c o n j u g a t e to R 0 . A s e t of

e l e m e n t s which a r e c o n j u g a t e to one a n o t h e r i s called a c l a s s .
E a c h e l e m e n t belongs to one c l a s s and only to o n e . H e n c e , the e l e m e n t s
of a g r o u p can be subdivided into d i s t i n c t c l a s s e s .
The i d e n t i t y e l e m e n t a l w a y s f o r m s a c l a s s by i t s e l f .
If a g r o u p i s A b e l i a n , i . e . if all its e l e m e n t s c o m m u t e , e a c h e l e m e n t
f o r m s a c l a s s by i t s e l f .
2.3. M a t r i x r e p r e s e n t a t i o n s — c h a r a c t e r s
If a s e t of m a t r i c e s R x , R 2 ... f o r m a g r o u p which i s i s o m o r p h i c o r
h o m o m o r p h i c to a g r o u p G, t h e s e m a t r i c e s a r e said to f o r m a r e p r e s e n t a t i o n
of G.
T r a c e s of c o n j u g a t e m a t r i c e s a r e e q u a l .
Proof:
Tr(Rc) = ^ г й (ст)
i
Tr(R0RT) = ^ r ; j (d)r j i (T)= T r ( R p R 0 )

i, j
T r f R p R ^ ' 1 ) = Tr(R0)
IAEA-SMR-12 / 2 1 13
Such a t r a c e i s c a l l e d a " c h a r a c t e r " and it h a s the s a m e v a l u e a s all the

e l e m e n t s of a c l a s s . U s u a l l y it i s w r i t t e n a s xR(cO-
If u n d e r the o p e r a t i o n s of the g r o u p a f u n c t i o n s p a c e (cp) t r a n s f o r m s
such as
(Ф) - R0(q>)
the m a t r i c e s R 0 f o r m a r e p r e s e n t a t i o n of the g r o u p and the f u n c t i o n s cp a r e
said to f o r m a b a s i s f o r the r e p r e s e n t a t i o n .
If S i s a n o n - s i n g u l a r m a t r i x and if the m a t r i c e s R 0 f r o m a r e p r e s e n t a t i o n
r R of G, then so do t h e m a t r i c e s R 0 = S R 0 S _ 1 . The two r e p r e s e n t a t i o n s r R
and Г р a r e c a l l e d e q u i v a l e n t r e p r e s e n t a t i o n s .
A r e p r e s e n t a t i o n is said to be r e d u c i b l e if it i s p o s s i b l e to find a m a t r i x S,
so t h a t a l l t h e m a t r i c e s of the c o r r e s p o n d i n g equivalent r e p r e s e n t a t i o n a r e
of the f o r m :
0
1m
R'o Jr n
0 R "0
w h e r e m and n do not depend on ст.

If it is i m p o s s i b l e to find s u c h a m a t r i x S, the r e p r e s e n t a t i o n is i r r e d u c i b l e .
The d e c o m p o s i t i o n of the r e d u c i b l e r e p r e s e n t a t i o n into i t s i r r e d u c i b l e
c o n s t i t u e n t s is s y m b o l i z e d by
(Гк o c c u r s CR t i m e s in the d e c o m p o s i t i o n of T w ) and can be e x p r e s s e d

a l g e b r a i c a l l y by t h e e q u a t i o n
x W(a) C rX R(cO
R
f o r all ст.
Schures l e m m a (Weyl's f o r m )
(a) If R 0 and Q 0 f o r m two i n e q u i v a l e n t i r r e d u c i b l e m a t r i x r e p r e s e n t a -

t i o n s of a g r o u p , and if a m a t r i x A ( s q u a r e , if p o s s i b l e ) e x i s t s s u c h t h a t
R0A = AQ0
f o r a l l a , then A = 0.
(b) If the m a t r i c e s R o f o r m a n i r r e d u c i b l e r e p r e s e n t a t i o n of a g r o u p
and if
R0A = AR0
14 FENEUILLE
f o r a l l ст, t h e n A i s a c o n s t a n t m u l t i p l i e d by the unit m a t r i x . It f o l l o w s f r o m

(a) t h a t , if R c and Q 0 a r e u n i t a r y and f o r m two inequivalent m a t r i x r e p r e -
s e n t a t i o n s of a f i n i t e g r o u p ,
X rij(CT)qVCT) = 0 for a11

j' and k
It f o l l o w s f r o m (b) t h a t , ' i f a l l the m a t r i c e s of an i r r e d u c i b l e r e p r e s e n t a t i o n

of a f i n i t e g r o u p a r e u n i t a r y , t h e n
^гу(ст)г*к(ст) = 6 ( i , i ) 6 ( j , k ) | -
0
w h e r e g i s the n u m b e r of e l e m e n t s of the c o n s i d e r e d g r o u p and n r i s the

d i m e n s i o n of t h e m a t r i c e s R o .
O t h e r f u n d a m e n t a l p r o p e r t i e s of f i n i t e g r o u p s (without p r o o f )
The n u m b e r of i n e q u i v a l e n t i r r e d u c i b l e r e p r e s e n t a t i o n s is e q u a l to
the n u m b e r of d i s t i n c t c l a s s e s of the g r o u p c o n s i d e r e d . If we d e n o t e by
x t C i T j ) the c h a r a c t e r of the m a t r i c e s c o r r e s p o n d i n g to the c l a s s C t within
the r e p r e s e n t a t i o n F j , then
Y [х-ЧС^фхССкГ,)] = -щ à (i,к)
j
£ NixíCirpxíqr,) = ga(M)
1
Ni = n u m b e r of e l e m e n t s of the c l a s s It f o l l o w s that if
х (с;г{) ^ C j x í q r j )
i
then
Cj " ~ ^ x(Cir{ ) x*(C;rj )
2.4. K r o n e c k e r product
L e t u s s u p p o s e that the n f u n c t i o n s фг , фj, ... фп f o r m a b a s i s of a r e p r e

s e n t a t i o n F x and that the m f u n c t i o n s ф1 ..., фе ..., фт f o r m a b a s i s of a
r e p r e s e n t a t i o n Гу of a g r o u p G. T h e n the m n f u n c t i o n s ф^ф t f o r m a b a s i s
of a r e p r e s e n t a t i o n T w which i s c a l l e d the K r o n e c k e r p r o d u c t (or the d i r e c t
p r o d u c t ) of t h e r e p r e s e n t a t i o n s Г х and Г and which i s w r i t t e n a s
r
w=rxxry=ryXF x
IAEA-SMR-12 / 2 1 15
If u n d e r an o p e r a t i o n of the g r o u p
i V
(ff)
"l/U
j.í
T h e r e f o r e xw(CT) = Хх(ст) x y ( a )-
L e t u s now s u p p o s e that Г х and Гу a r e i r r e d u c i b l e , T w i s u s u a l l y
r e d u c i b l e and can be w r i t t e n a s
The b a s i s f u n c t i o n s of Г к can be w r i t t e n a s l i n e a r c o m b i n a t i o n s of the

mn functions ф2
pk(Fß) =^(ГХ
jЛ
(the s y m b o l ß c h a r a c t e r i z e s t h e equivalent i r r e d u c i b l e r e p r e s e n t a t i o n s
if C s i s g r e a t e r than one). The i n v e r s e t r a n s f o r m a t i o n can be w r i t t e n a s
=
X(rs/3k|r*j; ryi)Pk(rsß)
к, s, ß
The c o e f f i c i e n t s ( ; |) a r e called C l e b s c h - G o r d a n c o e f f i c i e n t s . If the

f u n c t i o n s ф j , фе and pk(rsß) are normalized, they f o r m a unitary matrix
and:
( ; I) = (I ; )*
2.5. W i g n e r - E c k a r t t h e o r e m
T h i s t h e o r e m i s f u n d a m e n t a l in o r d e r to apply group t h e o r y to the

t h e o r y of a t o m i c s t r u c t u r e .
L e t u s s u p p o s e t h a t we have to evaluate the m a t r i x e l e m e n t
and t h a t the f o l l o w i n g conditions a r e s a t i s f i e d :

(1) t h e p f u n c t i o n s f o r m an o r t h o n o r m a l b a s i s f o r the i r r e d u c i b l e r e p r e -
s e n t a t i o n Г р of a g r o u p G;
(2) t h e q f u n c t i o n s tpj f o r m an o r t h o n o r m a l b a s i s f o r the i r r e d u c i b l e
r e p r e s e n t a t i o n r Q of G;
(3) t h e r f u n c t i o n s ву. f o r m an o r t h o n o r m a l b a s i s f o r the i r r e d u c i b l e
r e p r e s e n t a t i o n r R o f G;
16 FENEUILLE
(4) u n d e r the o p e r a t i o n of G, t h e q o p e r a t o r s h j t r a n s f o r m in a n i d e n t i c a l
m a n n e r to the b a s i s f u n c t i o n s ф : \
«л) - R f a H ^ ) (hjJ-RforHhjJRicr)-*
then
I h i I 9k ) = X A
ß <ГР ' Г 0 ' r R l r Q 3' r R k >
ß
3. T H E ROTATION G R O U P IN T H R E E DIMENSIONS
3.1. I n f i n i t e s i m a l r o t a t i o n s and a n g u l a r m o m e n t a
A l l the p o s s i b l e r o t a t i o n s w h i c h t u r n a s p h e r e into i t s e l f c a n be s t u d i e d ,
but f o r o u r p u r p o s e it i s s u f f i c i e n t t o c o n s i d e r i n f i n i t e s i m a l r o t a t i o n s (by
dee a b o u t a g i v e n a x i s Ç, f o r e x a m p l e ) . We d e f i n e the i n f i n i t e s i m a l r o t a t i o n a l
o p e r a t o r by
or
R ( d o , Ç) = 1 + idoTç +
Any f i n i t e r o t a t i o n about R ( a , f ) c a n be w r i t t e n in t e r m s of a and I In

fact
R ( a + d a , ? ) = R ( d a , ? ) R ( a , Ç)
= (1 + i d o ? ) R ( а , Ъ
t h u s 4- R ( q , ? ) = i I ,ь R ( S , П and t h e r e f o r e
da
R(e.?) = eial£
F I G . 1. D e f i n i t i o n o f l f - a x i s in t e r m s of a n g l e s 0 a n d tp.
IAEA-SMR-12 / 2 1 17
L e t u s now c o n s i d e r an i n f i n i t e s i m a l r o t a t i o n by do about t h i s a x i s can

be defined by t h e a n g l e s 0 and cp a s shown in F i g . l . We can e a s i l y s e e that
R ( d a , £ ) = R(do s i n 0 cos cp, x) R(da sin 0 s i n cp, y) R ( c o s 0 d « , z )
and t h u s
Iç = s i n 0 c o s cp I x + sin 0 sincp Iy + c o s 9 I z
So, t h e i n f i n i t e s i m a l o p e r a t o r s add like v e c t o r s and any r o t a t i o n can be

e x p r e s s e d in t e r m s of l x , ly and l z only.
We c o n s i d e r now a f i n i t e r o t a t i o n R(a, Çj), w h e r e Çj l i e s in the plane
(ÏÏy, Oz). F i g u r e 2 shows t h a t
Rfa.Çj) = R(0,i)R(a,z)R(-0,x)
Fig. 2. Finite rotation R(a, £,).
Then we have
1 + ia(I y s i n 0 + I z cos в) + 0 ( a 2 )
= [1 + i0 I x + O ( 0 2 ) ] [1 +ialz+ 0 (a 2 )] [1 - i 0 I x + O(0 2 )]
•whence i t f o l l o w s i m m e d i a t e l y t h a t
ily ~ Ixlz ~ I^^-X
and t h e r e f o r e
il x - I z I у - I y l z
18 FENEUILLE
o r , when we d e f i n e
I + = Ix + i l y , I. = I x - i l y
Uz.lJ = ± I±
[I + , I . ] = 2 I Z
CONCLUSION: The i n f i n i t e s i m a l o p e r a t o r s of t h e r o t a t i o n g r o u p in t h r e e
dimensions are angular momenta.
3.2. C l a s s e s and i r r e d u c i b l e r e p r e s e n t a t i o n s
The e i g e n f u n c t i o n s of I 2 and I z a r e
(Î) 2 | 7 I M > = 1(1+1) I 7 I M >

-I S M s I
Iz | 7 l M > = м | т 1 м >
I X | T I M > = a I 7 IM + 1 )> + b | 7 I M - l >
IУ 17 IM У = с I 7 IM + О + d | 7 I M - l >
Therefore
Ща, z ) | 7 I M > = e i a M | 7 l M >
B.(ß, î ) |7IM> = ^ a(/3, M') I 7IM 1 У

M'
T h u s , the (21 + 1) f u n c t i o n s I 7 I M ) f o r m a b a s i s of a r e p r e s e n t a t i o n f o r the
r o t a t i o n g r o u p in t h r e e d i m e n s i o n s . T h i s representation is irreducible
and denoted by D 1 .
B e f o r e d e t e r m i n i n g the c h a r a c t e r s of t h i s r e p r e s e n t a t i o n , we have to
find t h e c l a s s e s of the c o n s i d e r e d g r o u p . Figure 3 shows that
R(0,X) R ( a , f ) = R(a, R(0, A) Ç) R(0 Д )
R(0,X)R(a, ?)R(-0,1) = Ř(J,X) where X = R(0,X)|
All r o t a t i o n s t h r o u g h the s a m e angle belong to one and the s a m e c l a s s ,

i r r e s p e c t i v e of t h e a x i s about which any of the r o t a t i o n s i s m a d e .
To find the c h a r a c t e r , it i s convenient to c h o o s e the z - a x i s . T h e n
the r o t a t i o n m a t r i x i s d i a g o n a l , with i t s t r a c e given by
i s i n í (21 + 1)
giaM= ^ = I
a
sin 2
IAEA-SMR-12 / 2 1 19
Fig. 3 . C l a s s e s of groups c o n s i d e r e d .
H e r e it i s i m p o r t a n t to s t r e s s t h e following: if we c o n s i d e r only s p a t i a l
t r a n s f o r m a t i o n , it i s obvious that xà = Xa+2ir I i s n e c e s s a r i l y an i n t e g e r ,
but if we c o n s i d e r spin t r a n s f o r m a t i o n , I c a n be h a l f - i n t e g e r and then
Xa = ~ X a+2rr* R o t a t i o n s about a given axis by a and a + 2it a r e no l o n g e r
identical.
F i n i t e g r o u p s including spin t r a n s f o r m a t i o n s a r e called double g r o u p s .
3.3. K r o n e c k e r p r o d u c t s — 3j s y m b o l s
We c o n s i d e r the (2Ii + l ) f u n c t i o n s | y i I i M i > and the (2I 2 +1) f u n c t i o n s
| y 2 I 2 M 2 > . The (2Ij + 1 ) ( 2 I 2 + 1) f u n c t i o n s | M j > | ъ Ч Щ , > f o r m a b a s i s f o r the
1 12
r e p r e s e n t a t i o n D ' X D which is g e n e r a l l y r e d u c i b l e . In o r d e r to r e d u c e
i t , we take into account that
x
a xa =
[ e x P ( ^ i a ) + ••• + e x p ( - i l i a ) ] [exp(il 2 a) + ... + e x p ( - i l 2 a ) l
= [exp(i(l! + I 2 ) a ) + ... + e x p f - i d i + I 2 ) o ) l
+ [ e x p W ^ + I g - l ) a ) + ... + e x p t - i f l j + I 2 - l)a)]
+ [exp(i I I j - I 2 I a) + ... + e x p ( - i | I j - I 2 | a)]
Therefore
D ^ X D * 2 = D Il + I2 + ... +DI I i _ I 2 I
The r u l e f o r r e d u c i n g K r o n e c k e r p r o d u c t s i s t h e s a m e a s the r u l e f o r
coupling angular m o m e n t a .
We c a n f o r m a b a s i s f o r an i r r e d u c i b l e r e p r e s e n t a t i o n D 1
f j I-Ц - I 2 I á I S +I2)) f r o m thé f u n c t i o n s | y 1 I 1 M 1 > | 72I2 M2 >

20 FENEUILLE
Formally:
|7III72I2IM> =^<I1M1,I2M2|IM>| 7 I I1M1>| 7 2 I2M2>

M l , M2
The C l e b s c h - G o r d a n c o e f f i c i e n t s •(, | > can be found by applying I z , I + and I .

to the two m e m b e r s of t h e p r e v i o u s e q u a t i o n ; the f i n a l r e s u l t i s
< IjMJ, I2M2 |lM> = 6(Mj +M2,M)
y f (21 + IXIT + I 2 - I ) ! ( I I - М Г ) ! ( 1 я - M 2 ) ! (I+ M) ! (I - M) ! V

Л
U l i + 1 2 + 1 + 1)1(1+1! - I 2 ) ! ( I + I 2 - I 1 ) ! ( I 1 + M 1 ) ! ( I 2 + M 2 ) ! j
v Vf (Ii + M i + x ) ! ( I 2 + I - M i - x ) !
L ' x ! (I - M - x) ! (I j - MJ - x)!(I 2 - I + M j + x ) !
x
T h i s e x p r e s s i o n i s r a t h e r c o m p l i c a t e d , but e x h i b i t s a high d e g r e e of
s y m m e t r y . By w r i t i n g x = I - M - y, f o r e x a m p l e , we o b t a i n
 = ( - D ^ V ' O a M j . I 1 M 1 |I 2 I 1 im>
| I 2 I 1 I M > = (-1) 1 " 1 '" 1 2 | l ! l 2 I M >
In f a c t , it i s p a r t i c u l a r l y convenient to d e f i n e f r o m the C - G c o e f f i c i e n t s
n e w c o e f f i c i e n t s : the 3j s y m b o l s . T h e y a r e d e f i n e d by:
/ 3l 32 1з \ i - i .m -i
= ( - l ) J l Jz (2j3 + 1 ) Ч з х Г П ! , j2m2|j3-m3>
\ т ^ г т з /
F o r s y m m e t r y p r o p e r t i e s of 3j s y m b o l s s e e Ref.[6] , pp. 1 - 5 .
3.4. R e c o u p l i n g c o e f f i c i e n t s — n j s y m b o l s
See R e f . [ 6 ] , C h a p t e r 3 ( 1 , 2 , 3, 4).
MAIN P R O P E R T I E S O F 3 j - S Y M B O L S
h ^ h ) i-i-m, ,-1/2/. I. . . \
I I = (-1) Ij3 J <JlmlJ2m2lilJ2J3"m3>
\ mx m2 m3 /
i h h h \ / к Je 3i \ / 03 Ji к \
V m! m2 т 3 / \ m2 m3 m i / \ m 3 mi т г /
I A E A - S M R - 1 2/212 1
Jl J2 Jä i ,j / 32 Ji J3
I = J J1 + -12 + J3 I
m j m 2 m 3 / m 2 rri! m3
J1 J2 J 3 Jl J2 J3
Il + Jí + Js
(-1)
m -m-, -m, -m
l m
2 m
3 > q
Jl J2 J3 \ / Jl J2 Зз
[j 3 ] 5 ( m j , m ' j ) 5 (m^ , m ' 2 )
m mj m 2 m3/ \ m j1 m ; , m1 ,1
Х
з.
J3. 3
Jl 32 J3 Jl J2 J3
1
= [j3l <5 ( j 3 , j 3 ) 6 ( m 3 , m ^
m m m m m т
mi, m 2 > l 2 3/ l 2 'з>
MAIN P R O P E R T I E S O F 6 j - AND 9j-SYMBOLS
< ( J i j 2 ) j i 2 , j 3 , j Ij х-(J2J3) J23-J>
1/0 . . . . í J3 J J12
= Hji2nj23]}1/2(-l)Jl+)2+]s+J
1 J 2 J23 .
< (jiJ2)j12- (j3j4)j34,jl(j1j3)j13, (j2j4)j24,j>
JI J2 J 12
= Í[j 1 2 nj 3 4 ][j 1 3 ][j24n 1 / 2 j3 j4 j34
JJ J 2 J3 / J l h h
h h \ m
l m
2 Ml M2 Мз
ji je2 h J2 h h j3
, m
i ^2 / m
"Ml 2 Мз / \ M 1 2 m3 /
JL J2 J3 \ I 11 ^2 J3 \
т
. m
l m
3 M1 ~ß2 3 /
Jl J2 J3 h h £3 jl je 2 is
m
h hi -ßl m2 ц 3 l M2 -МЗ
22 FENEUILLE
ЗЗ •) Již J3 J J12
(W'tW • = 23^23 )
]2 J23 h Ьз
Jlz
J3 3 j12 J Г J1 3 J23 i3 J J12
J23 Ji J2 З23 J N 2 ^ 3 J31 J 2 Ói J31
a b c
= ( - l ) a + b + C {[b][c]}" 1/2
О с b
a b X
£ [x] (-1) ó(p,0)(-l) a + b {[a][b]} 1 / 2
b a p
a b x
2a + 2b
[x] (-1)
a b p
a b x с d x * e f x
£ ix](-l)X
с d p e f q b a r
p q r p q r
e a d .f b e
a f r
ra b X
1 Í e f x
2x
-l) Ы d q e
l с d Pj l a b r
p с b
a b x ' с d x ' e f x "J Г g h x
[x]
с d p e f q g h r J [ a b s
d q e 'h r e"
ly] p с b g b
a f у a
f У.
a f x" a f x
[x] [y] d q У d
q У = « ( р . р ' Ж с . с ' Щ р П с ] } -1
X.y
p с b p' c' b_
IAEA-SMR-12 / 2 1 23
' a f x
a f x с d X
2\
Tlx] d q e = (-1)
x e b X e f q
p с b
a b e
a b e
b+ c+ e+f
с d e (-1)' {[e][f]}" 1/2
d с f
f f 0
4. TENSOR O P E R A T O R S
4 . 1 . D e f i n i t i o n of i r r e d u c i b l e t e n s o r o p e r a t o r s
In the p r e v i o u s c h a p t e r we have s e e n t h a t t h e s t a t e s I Y I M ) have well-

d e f i n e d s y m m e t r y p r o p e r t i e s u n d e r the o p e r a t i o n s of the r o t a t i o n g r o u p in
t h r e e d i m e n s i o n s . H o w e v e r , this is i n s u f f i c i e n t f o r an a p p l i c a t i o n of t h e
W - E t h e o r e m , s i n c e the u s e of t h i s t h e o r e m r e q u i r e s o p e r a t o r s having
w e l l - d e f i n e d s y m m e t r y p r o p e r t i e s . One of t h e m o s t i m p o r t a n t c o n t r i b u t i o n s
of R a c a h has b e e n the d e f i n i t i o n of s u c h o p e r a t o r s .
I f , u n d e r the o p e r a t i o n s R 0 of a g r o u p , a f u n c t i o n ф b e c o m e s R 0 $ , an
o p e r a t o r T a c t i n g on ф b e c o m e s R 0 T R g 1 . We know a l s o that it i s s u f f i c i e n t
to s t u d y i n f i n i t e s i m a l r o t a t i o n s and we only have to find f o r o p e r a t o r s the
a n a l o g u e of the t r a n s f o r m a t i o n L ф. Since
il* . U m MfOLU
1 a
a-* n0
f o r o p e r a t o r s , t h i s equation t a k e s t h e f o r m
R(q
lim - f)TR(-g,f)-T = (l+ittIt)T(l-iaIE)-T = ,ц T]
a-» 0
So we s h a l l s e e that t h e ( 2 k + l ) o p e r a t o r s T<k) ( - k s q s k ) f o r m the c o m p o n e n t
of an i r r e d u c i b l e t e n s o r o p e r a t o r which t r a n s f o r m s as t h e i r r e d u c i b l e
r e p r e s e n t a t i o n D M (or of r a n k k) within t h e s p a c e defined b y T , if
[Iz,T<qk>] = q T ®
[ l i . T ® ] = [k(k + l ) - q ( q ± l ) ] 1 / 2 T ( q k ± > 1
T h e s e e q u a t i o n s a r e b a s i c f o r t h e t h e o r y of t e n s o r o p e r a t o r s .
4.2. Wigner-Eckart t h e o r e m
P o r the t h r e e - d i m e n s i o n a l r o t a t i o n g r o u p , the W - E t h e o r e m t a k e s a
v e r y s i m p l e f o r m , s i n c e we know t h a t D 1 d o e s not o c c u r m o r e o f t e n t h a n
24 FENEUILLE
once in the d e c o m p o s i t i o n of the K r o n e c k e r p r o d u c t D k X D 1 , T h e r e f o r e , we

can write
< o ' l ' M ' J T q k ' | a I M > = A ( a ' , I ' , k , a, I)
or
/к I Г \
< > ' I ' M ' | T ( q k ) | a I M > = (-1Г1+к - м ' [V]1^2 A
\q M -M'/
[x] = 2x + l
U s u a l l y we s e t
(•l)-I +k-I' [ Г ]1/2 А = < q , J , ||X(k)
w h e r e the f a c t o r ^ || || i s called a r e d u c e d m a t r i x e l e m e n t .
Thus t h e W - E t h e o r e m f o r t h e t h r e e - d i m e n s i o n a l r o t a t i o n g r o u p t a k e s
the f i n a l f o r m
.
<«ФМ'|Т<к>|в1М> = (-1)1_М
.( v k 1
\
<аЧ'||т№||о1>
\-M' q M /
We have- to m e n t i o n t h a t we can d e f i n e double t e n s o r o p e r a t o r s

Ck к }
^ Q i V having well-defined r a n k s kj and k 2 with r e s p e c t to two independent
a n g u l a r m o m e n t a I j and I 2 . The W - E t h e o r e m t e n s o r i s :
<a'r 1 I^M' 1 M^|T ( q k ' q k 2 ) | e I 1 I 2 M 1 M 2 > = ( - l ^ l + ^'-Mi-Mz

\
/ Г1 k l h \ / 4 k
2
\-M' M j \-Щ q 2 Щ/
4.3. Coupled t e n s o r o p e r a t o r s
F o r t h i s s e c t i o n , s e e Ref.[6], C h a p t e r 3.5, .6.
Fundamental formulas
1
x gC) = £ T(q ;!)U^)(k1q1,k2q2|k1k2KQ)
4l42
T (klk2)K = £ т ( к Л ) ( k i q i k 2 q 2 |klk2KQ)
4102
IAEA-SMR-12 / 2 1 25
Scalar product
(TOO.Utk)) = ^ ( ^ 1 ) - q T W u ( k ) = (_i)k [ k ]+V2 { T (k) u<k) }(0)
T (k-k) = (_l)k[ k ]l/2 T(kk)0
Matrix elements
If T ' k i ' and U(kz) a c t on p a r t s 1 and 2 of a s y s t e m , r e s p e c t i v e l y , then
к
'il il Г
< Í l Í 2 J l l X Q > l l i i ^ J , > = { [ J H J ' H K l } 1 7 ^ j2 jfe k 2
.J J' K.
x<j1||T(k.)||ji><j2||T(k2)|^>
F o r double t e n s o r s , t h i s f o r m u l a r e a d s
k
il i'l l
<7j1J2j||T^k^K||yj- = {[JHJ'HK]} 1 / 2 h i2 k
2
IJ J1 К .
x <7 U a l l T ^ J J I v j i i p
Important special cases
< j 1 j 2 J M J |(T<k> -U< k ))| j^jJjJ'MJ >
J
i'l Ъ
= (-l)ii' + i2+J 5 ( J , J ' ) 6(Mj, Mj' )
k
Í2 i l
X < j 1 | | T W | | j . > < j 2 IIUW | | j . >
F o r an o p e r a t o r a c t i n g only on p a r t 1 we c a n w r i t e
<j1j2j||T(K) ||j'j'J<> = 6(j2,j-)(-l)Ji + b+J,+k
J к J'
x{[J],[J']}1/2 <ill|TW||j-1>
J1 32 jj
26 FENEUILLE
[valid f o r T ( k 0 ) if we r e p l a c e the r e d u c e d m a t r i x e l e m e n t of the r i g h t - h a n d

s i d e of the equation by < y Í ^ II т ( к 0 ) II T'J'i^ ^ • F o r an o p e r a t o r U( k ') a c t i n g
only on p a r t 2 we have
Ü +ji + J + k'
< jlj2Jl|U(k,)||jiji,J'> = Ô ^ J ' ^ - l )
fJ k' J1 1
1/2
x{[J][J-]} <jJ|u(k')||j'>
[valid f o r T( o k ) if we r e p l a c e the r e d u c e d m a t r i x e l e m e n t on the r i g h t - h a n d

side of the equation by < y j || T«*) || y ^ j. >].
4.4. Elementary tensor operators
4.4.1. Angular momentum
JW
U = J &. J(D
1 = + J ( « = 2-1/2J
< J II J H J > = { J ( J + l ) ( 2 J + l)} 1 /2
4.4.2. Spherical harmonies

11/2
С(Ю = i - 4 7 r l v «
q 1 2k+ l j 4
£ к
0 | | c ( q k ) | U ' > = (-1){ШП1']}1/2
\ О 0 0 j
J IЛ-i' \ S к s и+Р)
[ к s a m e p a r i t y a s {£. + £.')
It i s s o m e t i m e s u s e f u l to r e p l a c e C^ k 'f(r) by
CO
C(qk)(ni,n'i') J Rnt(r)f(r)Rn,c,dr
0
ni.n'i'
where
< n a i a II СW ( n í , n'Г> ) II n b i b > = б (n, n a ) 6 ( i , 1 a ) б (n-, n b ) 6 (I '-, i b ) 
4.4.3. Linear momentum
The g r a d i e n t v e c t o r is a t e n s o r o p e r a t o r of r a n k 1 a c t i n g on the o r b i t a l
s p a c e only; it can be r e p l a c e d by (see 4.5.3)
IAEA-SMR-12 / 2 1 27
X С « M , , , ) / R „ { ( r ) - ^ +
0
ni.n'i"
4 . 4 . 4 . Double t e n s o r s
It is s o m e t i m e s convenient to i n t r o d u c e the following t e n s o r o p e r a t o r s

W<xk> ( n i , n ' i ' ) and v W i n i . n ' i 1 ) d e f i n e d by
< n a s i a II w^xk' ( n i , n ' i ' ) II n b s i b ) = ó ( n a , n ) 6 ( í a , i ) 6 ( n b , n ' ) 5 ( j e b , i ' ) { k ] [ k ] } 1 / 2
V ( k > ( n i , n ' i ' ) = 2 1 / 2 W< 0 k >(n.e,n'i') .
4.5. Atomic interactions under tensorial f o r m
4.5.1. Coulomb i n t e r a c t i o n
e2
- V eo2 r< /r'k> • r (k) \
r
r / 7r Ш " 2 i
12 V >
к
t h i s o p e r a t o r c a n be r e p l a c e d by
R ( k > ( n i , n ' i ' ; n " i ' ' , n ' ' ' i ' ' ' ) ( C < k > ( n i , n " i " ) • Cř, k >(n'í',n'"i"'))
ni.n'i'
n"í",n",í"'
where
. R ( k ) ( n i , n ' i ' ; n " i " , n ' " i ' " ) = f f e2(RnCRn.r)i(RnTRn"i")2 7|Tdrldr2
U s u a l l y we w r i t e
R ( k ) ( n i , n ' i ' ; n i , n ' i ' ) = F ( k ) ( n i , n ' i ' ) ; R ( k ) ( n i , n ' i ' ; n'SL', n i ) = G ( k ) ( n í , n ' i ' )
4.5.2. Spin-orbit interaction
T h e s p i n - o r b i t i n t e r a c t i o n can be w r i t t e n a s
S(r)(s -1)
It can be r e p l a c e d by:
^ Ç(ni,n'i){i(i + i)(2í + l)/6}1/2W<bl>(ni,n'i)

ní,n'i'
where
Ç(ni,n'i) =J RníRn,^(r)dr
О
2 8 FENEUILLE
4.5.3. Exercise
Give in t e n s o r i a l f o r m :
(a) the magnetic spin-spin interaction
s x • s g _ 3(r 1 2 • s 1 ) ( r 1 2 - s 2 )
. 5
12 12
(b) t h e i n t e r a c t i o n b e t w e e n spin and a n o t h e r o r b i t
VI ( — )X Pl (s 1 + 2 s 2 ) + V
2 — JXp 2 (s 2 + 2 s x )
12 •12
Show t h a t
V = -(2)1/2±{C<W +|;C(1)
(illicooijoo j i . , = i ( i + 1 )
[ 2
k
k
(
(
k
2 i ;^ , + 1 )
( i ï C « ||i>)
5. CONFIGURATIONS WITH TWO E L E C T R O N S
5.1. L - S coupling
5.1.1. N o n - e q u i v a l e n t e l e c t r o n s
The b a s i c f u n c t i o n s a r e of the type
Iу(ИЛ') SLJM)>
o r , if we t a k e into account the p r i n c i p l e of a n t i s y m m e t r y
(l/2)1/2{|T(i1X^)SLJM> - lYtijû^SLJM»
= (l/2)1/2{|7(i1i^)SLJM> + (-l)s +L + í + r |7(íj,í2)SLJM>}
U s i n g the g e n e r a l f o r m u l a given in s u b s e c t i o n s 4 . 3 , 4 , 5 we obtain
e2
< y ( l V ) SLJM 7(4.2') S ' L ' J ' M ' ) = ô (J, J ' ) б (M, M1 ) 5 (S, S' )
£ £ к
X б (L, L ' ) J J ^) FF kk (( ií ,, £')
£') -j j (• ( - l ) L + { + r
V V L
l.k even < m i n ( 2 £ , 2£')
X<i||C(k) ||i>< V ||c(k) ||i'>

IAEA-SMR-12 / 2 1 29
[i i' к
Gk (i, V ( - l ) s 2
li i' К
same parity as (í + С')
T h e m a t r i x e l e m e n t s of the s p i n - o r b i t i n t e r a c t i o n
Л S(rj)(ij •/,) (i = l , 2 )
i
can be obtained in t h e s a m e way:
<7(ii') SLJMjAîi'JS'L'J'M') = Ô(J, J') Ó(M,M') ( - l ) s ' + L + I + { + t ' + 1

S S' 1
J {[Ll[L'llSl[S<l}1/2JJ | ? i { i ( i + l ) ( 2 i + l ) 1 / 2 ( - l ) s ' + L'
.L' L J.
S 1 S'l fL 1 L'
X- + Ç s . { i ' ( i ' + l ) ( 2 i ' +l)}!/2 (-1 ) S + L
i2 i2 i
2 i i' i
S 1 S'l fL 1 L'
i 1 i i i'
2 2 2
where = Ç(ni,ni) and = Ç (n'i<, n'i').
5.1.2. Equivalent e l e c t r o n s
The m a t r i x e l e m e n t s a r e obtained in e x a c t l y the s a m e way a s in the

p r e v i o u s s e c t i o n , but now the b a s i c f u n c t i o n s r e a d
| T i 2 S L J M > = | { l + (-l)L+s}|7i1je2SLJM>
and we s e e i m m e d i a t e l y that S + L m u s t be e v e n . F i n a l l y we obtain

,2
< y i SLJM y i2 S'J'J'M' У = 6(J,J')6(M,M')6(S,S')6(L,L')
12
i i к
x £ P k (i)(-i) L I <i||c<k> ||i> 2
к <2í
i L
even
< 7 Í 2 S L J M | A | 7 Í 2 S ' L ' J ' M ' > = 26(J, J ' ) 6 ( M , M ' ) ( - 1 ) S ' + L + J + 1
30 FENEUILLE
X Ç i { [ L ] t L ' ] [ S ] [ S , ] } 1 / 2 { 3 / 2 i ( i + 1)(2Í + 1)} 1 / 2
js S' 1I f S 1 S' j Г L 1 L'

X
lb' L jJ [ H I J Ь i Jř
5.2. j - j c o u p l i n g
The c o r r e s p o n d i n g f o r m u l a s can be o b t a i n e d by m e a n s of the s a m e

t e c h n i q u e s a s u s e d f o r L - S c o u p l i n g . The b a s i c f u n c t i o n s a r e now of t h e
type
•yiji'j'JM) =-^||T(ij)1(jfj')2jM> -(-D^^'lTOe'j'M^JM)}-
|7(ij)2 JM> = H l + ( - l ) I } | 7 ( i j ) i f i j ) 2 J M >
a n d , f o r e x a m p l e , we o b t a i n
5 . 3 . V a l i d i t y of v a r i o u s c o u p l i n g s
T h i s q u e s t i o n w a s a l r e a d y d i s c u s s e d in c h a p t e r 1. In p a r t i c u l a r , if we
do not t a k e into a c c o u n t n u c l e a r e f f e c t s , we know t h a t t h e only good q u a n t u m
n u m b e r s a r e J , M and p a r i t y . M o r e o v e r , we s u p p o s e in t h i s s e c t i o n t h a t a
o n e - c o n f i g u r a t i o n m o d e l i s a p p l i c a b l e . T h e n , if the e f f e c t s of s p i n - o r b i t
i n t e r a c t i o n a r e s m a l l with r e s p e c t to t h o s e of C o u l o m b i n t e r a c t i o n , we c a n
c a l c u l a t e t h e e f f e c t s of Л f o r A given t e r m . In t h i s c a s e S and L a r e good
a p p r o x i m a t e q u a n t u m n u m b e r s and s i n c e t h e J - d e p e n d e n c e of
< 7 S L J M | a | 7 S L J M > i s c o n t a i n e d in
we c a n w r i t e :
E ( 7 S L J ) - E ( 7 S L J - 1) = J A ( a SL)
T h i s i s the w e l l - k n o w n L a n d é i n t e r v a l r u l e .
IAEA-SMR-12 / 2 1 31
On t h e o t h e r h a n d , if the e f f e c t s of C o u l o m b i n t e r a c t i o n a r e s m a l l with
r e s p e c t to t h o s e of s p i n - o r b i t i n t e r a c t i o n , j - j coupling i s a good a p p r o x i m a t i o n .
T h i s s i t u a t i o n i s e x t r e m e l y r a r e in a t o m i c s p e c t r a , but one e x a m p l e i s
p r o v i d e d by the c o n f i g u r a t i o n s 6 p 2 and 6 p 7 s of P b I.
U n f o r t u n a t e l y , v e r y o f t e n n e i t h e r L - S n o r j - j coupling a r e valid a p p r o x i -
m a t i o n s . In t h i s c a s e it is n e c e s s a r y to d i a g o n a l i z e the m a t r i x of C o u l o m b
i n t e r a c t i o n and s p i n - o r b i t a l i n t e r a c t i o n f o r e a c h v a l u e of J; the wave f u n c t i o n
i s a s u p e r p o s i t i o n of d i f f e r e n t b a s i c f u n c t i o n s : coupling is i n t e r m e d i a t e .
F o r noble g a s e s (one h o l e , one e l e c t r o n ) , h o w e v e r , a t h i r d type of coupling
p r o v i d e s a r a t h e r good a p p r o x i m a t i o n . T h i s i s j-k coupling which is d e f i n e d
by
|T(ij)i'k|JM>
(2{'*1) DOUBLETS
С
(2Í'«1) DOUBLETS
Fig. 4. j-k coupling.
[ 2 i -1)
TRIPLETS
( 2 ř «1)
С SINGLETS
TWO GROUPS OF (2i'»2) LEVELS
TWO GROUPS OF 2f LEVELS
>
L- S j-j
F i g . 5. L-S and j-j couplings.
32 FENEUILLE
O b v i o u s l y , t h i s coupling applies if
л(Я»<—»л(Л')
The c o r r e s p o n d i n g s p e c t r u m h a s the s h a p e shown in P i g . 4 (we a s s u m e

i ' S J i ) while the two o t h e r couplings would p r o v i d e the s c h e m e s shown in
Fig.5.
5.4. E l e c t r o n s in c l o s e d s u b s h e l l s
F o r t h i s s e c t i o n , s e e Ref.[4].
6. ANTISYMMETRY P R O B L E M S
6.1. N o n - e q u i v a l e n t e l e c t r o n s
L e t us c o n s i d e r , e . g . the c a s e of t h r e e e l e c t r o n s ( 1 , 2 , 3 ) in t h r e e d i s t i n c t
s u b s h e l l s (nj2)a , ( n i ) b , (n£) c :
m1/2
I a b с, тУ = "I "g г { | a i b 2 c 3 r> - b3 c2 т> + | a 2 b 3 C l r>
- | a 2 b 1 c 3 T > + | a 3 b j c 2 т > - | a 3 b 2 c x т > }
ill172
I a b с, т> = j g У { | a 1 ( b c ) 2 3 т> - | a 2 (bc) 1 3 т> + | a 3 (bc) 1 2 т>}
M o r e g e n e r a l l y we have
-|(a)"' (b)°Mc)"s ... O M C N ^ . . ^ 7 ( - l ) P x l ( a ) ; ; . . . i n (b)* ... т>

X
' 1 2
c
nn Nn n = —;—~t г » [N = ni1 + n 12 + . . . + nkk ]
i . 2 . ••• n k n ! n2 ! . . . n k !
p x i s the p a r i t y of t h e p e r m u t a t i o n P x given by
/ 1 2 N \
P =
k
••• ••• - V - nk,
P x = p r o d u c t of p x t r a n s p o s i t i o n s .
6.2. E q u i v a l e n t e l e c t r o n s — f r a c t i o n a l p a r e n t a g e c o e f f i c i e n t s
E l e c t r o n s in one and the s a m e s u b s h e l l can be indexed only if we s p e c i f y

all the q u a n t u m n u m b e r s d e f i n i n g the o r b i t , i . e . n, SL, m { , m s . In o t h e r w o r d s ,
IAEA-SMR-12 / 2 1 33
the wave f u n c t i o n s m u s t be w r i t t e n in t e r m s of Slater d e t e r m i n a n t s and we

a l r e a d y know t h a t t h i s p r o c e d u r e i s u s u a l l y v e r y t e d i o u s . In o r d e r to avoid
the e x p l i c i t i n t r o d u c t i o n of d e t e r m i n a n t - p r o d u c t s t a t e s , R a c a h i n t r o d u c e d
the concept of f r a c t i o n a l p a r e n t a g e . It is b a s e d on the f o l l o w i n g p r i n c i p l e :
We d e f i n e the s t a t e s of the c o n f i g u r a t i o n s i N , i N _ 1 and l by the s e t s
of q u a n t u m n u m b e r s
7 SL Ms M l = Г2
7 SL M s M L s Л
m s m^ = и
Since e v e r y d e t e r m i n a n t - p r o d u c t s t a t e f o r an N - e l e c t r o n s y s t e m i s a s u m
of t e r m s , e a c h of which involving an e i g e n f u n c t i o n ^ N ( s i m s m e ) of the N - t h
e l e c t r o n , we m a y w r i t e :
|П> = u|n> |fi>|uN>

Q, uj
6.2.1. M a t r i x e l e m e n t of a s i n g l e - p a r t i c l e o p e r a t o r
< П | р | Г 2 ' > = N < n | f n | r 2 ' >
< í 2 | F | f i ' > = N ^ < Í2 [?2; to> u 1 | f t ' > 
If we a s s u m e that the p h a s e s of the v a r i o u s s t a t e s i n t r o d u c e d have b e e n

c h o s e n to m a k e s u r e that the c o e f f i c i e n t s a r e r e a l , t h e n
< Q |?T;u> = < |n>
6.2.2. Two-particle operators
A m o n g the ^ N ( N - l ) c o m p o n e n t s gij ( i > j ) c o m p r i s i n g G, t h e r e a r e

2 ( N - l )(N-2) which do not involve the N - t h e l e c t r o n . Hence we obtain "
< = [N/(N-2)]<Q| ^ g j ß ' )

jci^N
Then:
n
< ^ gij l ' > = ^ < ŠT | ? 2 ; t o > < Г 2 " ; ш | Г2' > < ? T | G | ? T ' >
-» chain c a l c u l a t i o n .
34 FENEUILLE
6.2.3. Fractional-parentage coefficients
< y Š L M S M L ; £ m s m { \y S L M s M L > = < Š M S s m j š s S M s >
X<LM L lm,|Lf L ML>< y Š b|}£N 7 S L>
T h e l a s t t e r m i s t h e c o e f f i c i e n t of f r a c t i o n a l p a r e n t a g e . The c a l c u l a t i o n
of t h e s e c o e f f i c i e n t s f o r d and f e l e c t r o n s r e q u i r e s s o p h i s t i c a t e d t e c h n i q u e s
w h i c h we s h a l l not d e s c r i b e h e r e . In a n y c a s e , the c o e f f i c i e n t s have b e e n
t a b u l a t e d by N i e l s o n , C . W . and K o s t e r , G . F . in " S p e c t r o s c o p i c c o e f f i c i e n t s
f o r t h e p n , d n and f n c o n f i g u r a t i o n s " , M . I . T . P r e s s , C a m b r i d g e , M a s s . (1963).
F o r p N e l e c t r o n s , t h e s e c o e f f i c i e n t s c a n be e a s i l y o b t a i n e d f r o m the r e l a t i o n
L 1 L' S I S'
2
^{[L][S]} V 2 -
SL
1 1 L
f o r odd S1 + IV
S i n c e the c o e f f i c i e n t s ; | У c a n be d e c o m p o s e d i n t o C - G c o e f f i c i e n t s and
C F P c o e f f i c i e n t s , we m a y w r i t e
|ÜN7 S L M s M l > = £ <£N"17SL|}£N7SL>

yŠL
X I 7 Š L , £N , i N 7 S L M s M L >
6.2.4. E x a m p l e s of a p p l i c a t i o n
S g i n - o r b i t i n t e r a c t i o n in ÜN - c o n f i g u r a t i o n s
^ (Si • ) =Л
N N
< Í 7 S L J M , |A|Í 7 ' S' L 1 M } > = Ó(J, J ' ) Ô ( M J , M , J ) ( - 1 ) S 4 L +J
'S S' 1
X - <ÍN 7 S L||W(u'||Ín 7' S' L - >
. L1 L J J
X ( < % S L ||W ( 1 1 ) | | i N 7' S' L 1 У

N 1
^ <£ " 7' S 1 L ' |} £ N 7 ' S ' L ' X tf S BIL^N-1 Y S L >
= N y Š L
y'S'L'
X<ín"17ŠL, íNJ £N 7 s LIIW^dIIín- 1 ^ š1 D.jlx? S- L > >

I A E A - S M R - 1 2 / 2 1 47


S 1 S' L 1 L'
= 35(7,7') e(S.S') ô(L,L')
_ s Š s i L i
S +
X (-1) Š^ + L + L + Í { [ s ] [ s , ] [ l ] 1 l , ] } 1/2
Coulomb i n t e r a c t i o n in mixed configurations of the_t^£e '
Definition of the coupling s c h e m e :
|I N
7 S L, V 7 S L J Mj >
T h r e e types of o p e r a t o r s :
G(i) = ^ F k ( i ) (C(k)(i,i) • C(k)('i,i))

i> j
G d (i,i') = ^ F k (i,i')(ci k )(i,i)-C( k )(i',i')+C( k )(i',i')-C( k )(i,i))

i> i
G e (í,í') = ^ G k (i,i') (C| k '(í,í') • Cf k '(i',i) + C( k )(i'.i)-C^)(i,i'))

i> J
N
|i 7 S L i ' S L J Mj>
= (
{ n T i F I "1)Pxl(# C
> l . . . x - l x + l . . . N + l n S L J M,>
X
= ШТЩ72 I ("D P x I < ^ 7 Š L|} 7 S L>

X y S L
X |[(iN-! ŤŠL)liiiHltli , Vl]ÍŠL, i- SL JMj>
Calculation of the exchange p a r t :
I K i N _ 1 7 Š L ) ! . . . N . l f i N ] y S L , I ' t l , S L J Mj >
= (S|)S, 1, s|§(| |)S,S><L(i,i')L L I (L i)L V L>

SL
X I [(i N _ 1 7 Š L) 1 N SLJM,)
< [ ( i N " 1 7 ' g- L ' ) ^ ^ , i N + 1 ] 7 ' S' L ' , S' L' J ' M'j I
36
< (S" j ) S1, S1 |S' (I | ) S ' S ' X (L1 i) L' £' L' |L'(Î V) L' L'>
S'L'
X (_1)S,+L'+1 + ( j e N-l-, g, L ' ) 1 i < î N . i . [ Î ' n Î j j ^ I S ' L ' . S ' L 1 J ' M
At.V) = ^ G k (i.i-) 2
Finally we have

= ^ G k ( í , i ' ) Ó(J, J ' ) ô ( M j . M J ) fi(S.S') 6 ( h , L ' )

к
X^ N <( 7 Š L | } £ N 7 S L>

ySL
S 2 ^1 fS 2 L 1 L L J L1
1 1/2
X ^ {[§'][§][L][L ]}
SL 2 S S J 12 SS Г L L,J L ' L L
i Л' к
X {[S][L]} - < Í N 7 ' S1 L'{ | y § L>
L L l
X 6(S,S')Í L' L V <i||c< k > ||£'> 2 {[Ь][Ь']} 1/2 (-1) У
.t l' к
Exercise: determine z and y.
6.3. Second quantization
For this section see Ref.[8] .

Basic relations:
IAEA-SMR-12 / 2 1 37
=44 ... вТ|0> = {aß ...v}
< о | а и ... a ß а а = { a ß ... и}*
[at, a t]+ = О
[ a £ . a 4 ] + = 0 .
[ a y , a | ] + = <5(7,Л)
ay|0> =О
f =
p = X i Z
1
Ě . 7,
G = g = a
\ zL ij \ /L l a í aAaC 
i/J E. T). £ . X.
7. STATIC F I E L D S
7 . 1 . U n i f o r m m a g n e t i c field
7.1.1. The G r o u p C„ . S y m m e t r y of t h e p r o b l e m
When the a t o m i n t e r a c t s with an e x t e r n a l u n i f o r m m a g n e t i c f i e l d , gť,

t h e s p e c i a l s y m m e t r y i s d e s t r o y e d and only the c y l i n d r i c a l s y m m e t r y (C œ )
r e m a i n s . The p a r i t y s t i l l is a good quantum n u m b e r , but J i s t h i s no l o n g e r :
only J z c o m m u t e s with t h e H a m i l t o n i a n and the e n e r g y l e v e l s can then be
c h a r a c t e r i z e d by M, an i n t e g r a l o r h a l f - i n t e g r a l e i g e n v a l u e of J z . The
l e v e l s a r e no l o n g e r d e g e n e r a t e (except s o m e t i m e s by a c c i d e n t ) . If the
m a g n e t i c field i s s u f f i c i e n t l y weak ( Z e e m a n e f f e c t ) , J can s t i l l be c o n s i d e r e d
a s a good q u a n t u m n u m b e r ; when t h e atom i n t e r a c t s with t h e m a g n e t i c f i e l d ,
e a c h l e v e l E y j i s s p l i t up into (2J + 1) l e v e l s E ? J M . E x p e r i m e n t a l l y , this
s p l i t t i n g p l a y s an i m p o r t a n t r o l e in the d e t e r m i n a t i o n of J of a given l e v e l .
In f a c t , t h i s m e t h o d was b a s i c to the d i s c o v e r y by S o m m e r f e l d of odd
m u l t i p l i c i t i e s in a t o m i c s p e c t r a and s t i l l i s f u n d a m e n t a l f o r the i n t r o d u c t i o n
of spin in o r d e r to i n t e r p r e t h a l f - i n t e g r a l v a l u e s of a n g u l a r m o m e n t u m .
When the m a g n e t i c field b e c o m e s s u f f i c i e n t l y s t r o n g , J is no l o n g e r an
a p p r o x i m a t e l y good q u a n t u m n u m b e r ( P a s c h e n - B a c k e f f e c t ) ; in o r d e r to
i n t e r p r e t the s t r u c t u r e s which a r e t h e n o b s e r v e d , it i s n e c e s s a r y to p e r f o r m
a quantitative analysis.
7.1.2. Quantitative a n a l y s i s
The H a m i l t o n i a n d e s c r i b i n g the i n t e r a c t i o n b e t w e e n an a t o m and the

m a g n e t i c field r e a d s
H
M =
38 FENEUILLE
w h e r e д м i s the m a g n e t i c m o m e n t of the atom and is given by,
- /3 (L + 2 S)
If we let the z - a x i s coincide with we obtain
H M = ( S ^ ( L Z + 2 S Z ) = ßgf(Jz +S Z )
In LS coupling, it i s p a r t i c u l a r l y e a s y to obtain the m a t r i x e l e m e n t s of

H M , since
< Q S L J M | J z | a ' S ' L ' J ' M ' > = M б (M, M') 5 (a, a' ) 6 (S, S' ) 6 (L, L 1 ) б (J, J 1 )
/ J 1 J' \
< a S L J M | S Z | a ' S ' L ' J ' M ' > = (-1) J " M
\ -M 0 M' /
X < o SLj||s||a'S'L'J'>
< a S L j | | s | | e ' S ' L ' J ' > = ô ( a , a ' ) 6 ( L , L ' ) é ( S , S')
f j 1 J 4
X (-1) L + S + I'+1 {[j][J.]}1/2 {S(S + 1)(2S+1)} 1 / 2 \ L
[ S L S J
If the m a g n e t i c field is sufficiently weak, we m a y use a f i r s t - o r d e r p e r t u r b a -
tion a p p r o x i m a t i o n and we have to c o n s i d e r only the c a s e of J = J ' . Then we
can w r i t e
/ J 1 J \
(-1) J " M = M{J(J + 1)(2J + 1)}" 1/2
\ - M 0 M /
J 1 J
_ , -, >s + L +j L(L + 1) - S(S+1) - J(J + 1)
1
' 2{J(J + l ) ( 2 J + l)}l/2 {S(S + l)(2S+l)}!/2
. S L S .
so that
< a S L J M l H M l a ' S ' L ' J ' M ' ) = б (M, M') б (а, а' ) 6 (S, S1 ) б (L, L' ) Xg(SLJ) M
w h e r e g(SLJ) i s the Landé f a c t o r :
_./ст T\ - -, , J ( J + 1) + S(S + 1) - L(L + 1)

g(SLJ) - 1 + 2J(J + 1 )
T h i s well-known r e s u l t could have been obtained in a m u c h l e s s s o p h i s t i c a t e d

way, e.g. f r o m the v e c t o r m o d e l , but t h i s model would not have yielded
the g e n e r a l f o r m u l a s p r e v i o u s l y obtained.
In the g e n e r a l c a s e , the wave functions | y J M ) > of a l e v e l E y j can be
written as
IAEA-SMR-12 / 2 1 39
|7JM> =^ ay(aSLJ)|aSLJM>
The e n e r g i e s of the Z e e m a n l e v e l s a r e then given by
EyJ + MgyJ ß g f
w h e r e the Landé f a c t o r i s e q u a l to
^ a 2 (a SLJ) g(SLJ)
Since g y J i s obtained d i r e c t l y f r o m t h e Z e e m a n s p e c t r u m it p r o v i d e s a t e s t
of the v a l i d i t y of LS coupling.
We c o n s i d e r now an LS m u l t i p l e t ; if ßg? is not n e g l i g i b l e with r e s p e c t
to A ( a S L ) , it i s n e c e s s a r y to d i a g o n a l i z e the m a t r i x of V s o + H M f o r a l l the
s t a t e s | a S L J M > . As we know t h a t M i s a good q u a n t u m n u m b e r it is s u f -
f i c i e n t to d i a g o n a l i z e t h e m a t r i c e s c o r r e s p o n d i n g to a given v a l u e of M.
If b e c o m e s m u c h m o r e i m p o r t a n t than A ( a S L ) , t h i s d i a g o n a l i z a t i o n can
be p a r t i a l l y avoided by u s i n g the b a s i s | a S L M s M L ) > within which H M i s
d i a g o n a l . V s o i s t h e n t r e a t e d by f i r s t - o r d e r p e r t u r b a t i o n t h e o r y ; the
c o r r e s p o n d i n g s t r u c t u r e i s a P a s c h e n - B a c k one.
Exercise:
Build up the m a t r i x of Vso + within the s t a t e s L S J M f o r a 2 P .
D i a g o n a l i z e t h i s m a t r i x . D e t e r m i n e the v a l u e of {ßgif/A(a SL)} f o r which
t h e r e a p p e a r s an a c c i d e n t a l d e g e n e r a c y (level c r o s s i n g ) .
7.2. U n i f o r m e l e c t r i c field
7.2.1. The g r o u p C „ r S y m m e t r y of the p r o b l e m
As in the p r e v i o u s c a s e , the s y s t e m a t o m plus field h a s no l o n g e r

s p h e r i c a l s y m m e t r y ; J is not a good q u a n t u m n u m b e r . H o w e v e r , the
s y m m e t r y i s not the s a m e a s in the p r e v i o u s c a s e ; i n s t e a d of c y l i n d r i c a l
s y m m e t r y , we have now c o n i c a l s y m m e t r y . The f i r s t c o n s e q u e n c e is that
p a r i t y i s no l o n g e r a good q u a n t u m n u m b e r . M o r e o v e r , we a r e going to
show that the i r r e d u c i b l e r e p r e s e n t a t i o n s of the c o r r e s p o n d i n g s y m m e t r y
g r o u p ( r o t a t i o n s about t h e field and r e f l e c t i o n s with r e s p e c t to an a r b i t r a r y
plane c o n t a i n i n g the f i e l d ) can be l a b e l l e d by the a b s o l u t e v a l u e s of M;
+M and - M being a s s o c i a t e d with a single r e p r e s e n t a t i o n , t h e n , f o r M ^ 0,
a double d e g e n e r a c y r e m a i n s .
L e t u s d e f i n e t, the r e f l e c t i o n o p e r a t i o n and R ^ , the r o t a t i o n about the
f i e l d . F i r s t it i s o b v i o u s that
M o r e o v e r we have
R„|7M> = e1M*|7M>
R | 7 -M> = е ш ? | 7 -M>
40 FENEUILLE
so t h a t
tRj TM> = R . ^ t I f M ) = eiMv | у М >
and
11 у м ) = | т -M>
It f o l l o w s that | t M ) > and | y - M ^ belong to the s a m e i r r e d u c i b l e

representation.
When t h e a t o m i n t e r a c t s with a u n i f o r m e l e c t r i c f i e l d , e a c h l e v e l E y j
i s s p l i t into (J + l ) S t a r k l e v e l s (if J i s an i n t e g e r ) o r into ( J + i ) S t a r k l e v e l s
(if J i s a h a l f - i n t e g e r ) .
We have a l r e a d y m e n t i o n e d that the p a r i t y i s no l o n g e r a good q u a n t u m
n u m b e r . We a r e going to show t h a t , b e c a u s e of t h i s f a c t , t h e f i r s t n o n - z e r o
t e r m in t h e p e r t u r b a t i o n e x p a n s i o n i s p r o p o r t i o n a l to the s q u a r e of the e l e c t r i c
f i e l d . H o w e v e r , t h i s i s not t r u e in the c a s e of a c c i d e n t a l d e g e n e r a c y a s in
the h y d r o g e n s p e c t r u m f o r e x a m p l e .
7.2.2. Q u a n t i t a t i v e a p p r o a c h of t h e S t a r k e f f e c t
The H a m i l t o n i a n d e s c r i b i n g the i n t e r a c t i o n b e t w e e n an a t o m and a

u n i f o r m e l e c t r i c field (in the dipole a p p r o x i m a t i o n ) r e a d s
H
E =
-е-Де
w h e r e ß e , the e l e c t r i c dipole m o m e n t of the a t o m , i s given by - e £ ) r j (the

s u m r u n s o v e r the e l e c t r o n s of t h e atom). In a f i r s t a p p r o x i m a t i o n the
p e r t u r b i n g e n e r g y i s given by
ee z < 7 J M | Z | 7 J M ' > {Z = £ z;}

i
F r o m p a r i t y c o n s i d e r a t i o n s we know that t h e s e m a t r i x e l e m e n t s a r e a l l z e r o .
It i s t h e r e f o r e n e c e s s a r y to c o n s i d e r the s e c o n d - o r d e r t e r m
e2 2 V < Y J M [ Z | Y ' J ' M > < Y 1J' M | Z I 7 J M )

L E(yJ) - E(y' J )
У'Г
H e r e the s u m r u n s o v e r a l l s t a t e s whose p a r i t y i s opposite to | y J M X
We s h a l l s e e t h a t the m a t r i x e l e m e n t s < Y J M | z | Y ' J ' M ' > a r e the s a m e
a s e n c o u n t e r e d in the p r o b l e m of e l e c t r i c dipole t r a n s i t i o n probabilities
and we s h a l l d i s c u s s t h e i r p r o p e r t i e s in the c o r r e s p o n d i n g chapter.
8. F I E L D QUANTIZATION AND RADIATIVE PROCESSES
8.1. Quantized f r e e e l e c t r o m a g n e t i c field
8.1.1. The c l a s s i c a l f i e l d
P o r a f r e e f i e l d , M a x w e l l ' s e q u a t i o n s can be w r i t t e n as
IAEA-SMR-12 / 2 1 41
H = VX A e = -V0---I-A
С dt
9 1 3
•V2</> - A | - ( V . A ) = 0
с dt
It i s p o s s i b l e to i m p o s e s i m u l t a n e o u s l y (V- Ä) = ф = 0 so that
^ = VXA
• A =0
- = i эА
e
" с 9t
A can be written in t e r m s of m o n o c h r o m a t i c t r a n s v e r s e plane waves
A = N"1/2^ {a(k,ü)U(k,ü)+a*(k,üj)U*(k,ü)}
kw
Ü(k,<3) = î ^ e ' ^ ^ , j - ^ a ( S , û ) + k 2 c 2 a(£,ü)} = О
[ e ® = polarization vector, linear or circular]
( k - e ® ) = 0
e = N" 1 / 2 > k(i a ( k , u ) U ( k , u ) + c.c.)

kra
'= N" 1 / 2 {i a (îc,u)[5x Ü(k,u)] + с.с.}
The field e n e r g y is
Ef i e 2 dT =
= b f f f f ä ^
{Volume of the cell in which the emf is localized}
The field m o m e n t u m i s
4 2 FENEUILLE
i.1.2. Canonical f o r m a l i s m
L e t us d e f i n e
Qjf- = ( а ( £ , й ) - а * ( Й , й ) )
P = Q(k u) =
iTö Ii ' " i k c ( a ( k u ) - a*(kw))
kD
H F i s a H a m i l t o n i a n only if
Э— h = and then N = —^
9P 9t
kü
кш
T h i s is the H a m i l t o n i a n f o r a h a r m o n i c o s c i l l a t o r .
8 . 1 . 3 . H a r m o n i c o s c i l l a t o r and second q u a n t i z a t i o n
L e t u s f i r s t d e f i n e the c r e a t i o n and a n n i h i l a t i o n o p e r a t o r s f o r one

h a r m o n i c o s c i l l a t o r by
ьш=Нр2+"2Ч2}
P = [p,q] = - №
b+ = {2ftu}" 1 / 2 [ u q - i p ] Ь ш = { 2 З Д " 1 / 2 [ioq + ip]
[ b i . b j = -i
BOSONS
h J n > = (n + | ) h u | n >
b b n
£ J > = nln>
It i s quite e a s y to show (using the c o m m u t a t i o n r e l a t i o n ) t h a t
b j n > = n ^ l n - i )
b £ | n > = (n + l ) 1 / 2 | n + l >
IAEA-SMR-12 / 2 1 43
|n> = (n!)" 1 / 2 (b£) n |o>
I
vacuum state
o r ground s t a t e
bJo> = 0
If we c o n s i d e r N independent h a r m o n i c o s c i l l a t o r s ( u j . . . Uj ... w N ), the

corresponding equations read
t b ^ , b + . ] = 6<j.i). [ b t . , b t . ] = 0, 1Ь Ш .,Ь И .] = 0
H = Z Вы, (bt. Ь ш . + i )
j
| П 1 . . . П , . . . n N > = { П 1 ! . . . п л . . . n N ! } " 1 / 2 ( b i p ... ( b t / N j o )
8.1.4. Q u a n t i z a t i o n of a f r e e e l e c t r o m a g n e t i c field
b l _ = { 2 f i w r 1 / 2 { u Q r _ - iP^_}
К UJ KOJ
bf_ = { 2 u/h}+1/2 a | _ . = hk(b|_
P l a n e wave: b e a m of n p a r t i c l e s , e a c h of t h e m having an e n e r g y e q u a l to
hw and a m o m e n t u m hit; t h e s e p a r t i c l e s a r e called p h o t o n s . We have to
s t r e s s that it would have b e e n p o s s i b l e to expand a l l the e l e c t r o m a g n e t i c
q u a n t i t i e s in t e r m s of s p h e r i c a l w a v e s (multipole f i e l d s ) . This r e p r e s e n -
t a t i o n i s well suited to c o n s i d e r the a n g u l a r m o m e n t u m of photons [7] .
8.2. General f o r m u l a s f o r transition probabilities
F o r t h i s p a r a g r a p h , s e e Ref.[9] , C h a p t e r s XVII, XXI.

P a r i s (1964) C h a p t e r s XVII, XXI.
Fundamental results
H = H0 + V
V i s the t i m e - i n d e p e n d e n t p e r t u r b i n g H a m i l t o n i a n and H 0 is the p r i n c i p a l

H a m i l t o n i a n [ e i g e n s t a t e s | a > , | b > ...]-. In a f i r s t - o r d e r a p p r o x i m a t i o n
44 FENEUILLE
W =<b|v|a>zXf(uba,t)
• W , ] 2
i sin- t
f ( u , t ) = t2 Ц 2 -
t - 00; f ( U , t ) - 2 7Г t б (CO )
^ = 2 X 2ir 6 (u)
The e n e r g y i s c o n s e r v e d d u r i n g t r a n s i t i o n s .
W a . b = 2 f pb Eb = Ea
pb = level d e n s i t y around the e n e r g y E b .
3.3. O n e - p h o t o n r a d i a t i v e p r o c e s s e s
5.3.1. H a m i l t o n i a n f o r an a t o m in an e l e c t r o m a g n e t i c field
• J i/j
kuj
In a P a u l i a p p r o x i m a t i o n (valid f o r dipole t r a n s i t i o n s and e l e c t r i c q u a d r u -

pole t r a n s i t i o n s )
=%r+ w z • ^ + {1
>•
+
w (Â ,2+
i S • ^
H can be r e w r i t t e n in the following f o r m : H = H 0 + H ^ j + H j + H n + Н ш where
н0 = ^ + — + magnetic t e r m s (spin-orbit interaction)

IJ
J
H = { ( Â ) + {Â ;
I l2b Pi' i j Pi)}
j
кш 3
IAEA-SMR-12 / 2 1 45
) + c
S I Z H ^ • ^ - 4
H III ^ (Aj) 2 = t e r m s involving ^ ^ (b + b + bb + )

2цс'
l e v e l s h i f t (not c o n s i d e r e d h e r e ) .
8.3.2. A b s o r p t i o n , induced and s p o n t a n e o u s e m i s s i o n
H] + H t I a r e t i m e - i n d e p e n d e n t p e r t u r b i n g H a m i l t o n i a n s d e s c r i b i n g t r a n s i -
t i o n s b e t w e e n the s t a t e s of the u n p e r t u r b e d H a m i l t o n i a n H 0 + H R a d . The r a d i a -
tion s p e c t r u m i s a s s u m e d to be continuous; it is then p o s s i b l e to d e f i n e
t r a n s i t i o n p r o b a b i l i t i e s p e r unit t i m e .
In a f i r s t - o r d e r c o n s i d e r a t i o n o n e - p h o t o n t r a n s i t i o n s a r e obtained only
if we c o n s i d e r H j + H n .
- Ef < E f initial state E j + n photons

final state E f + (n-1) photons
Ef - E , = f t u f i Absorption
• E; > Ef initial state E j + n photons

final state E f + (n +1 ) photons
E; - E f fiuh. Induced e m i s s i o n
- E; > Ef initial state Ei

final state E f + 1 photon
E j - E f = fiUlf Spontaneous e m i s s i o n
8.3.3. Spontaneous e m i s s i o n
Initial state Et, |i//i>|o>
Pinal state E f + fiuif, 11//^ | k Jf ш )•
P h o t o n e m i t t e d in the d i r e c t i o n к with the p o l a r i z a t i o n e & l The

t r a n s i t i o n p r o b a b i l i t y p e r unit t i m e and p e r unit s o l i d - a n g l e is given by
2 Vu 2
w;j =£|<f|H I + Hn|i>|
2(2FF)3F, C 3
46 FENEUILLE
T = S T j
Tj = | ( p j . + ift(Sj • { £ x e ® » ! e
W
if |<*f|T(S.i3)K>|2
Usually ( k - r ) « 1 for atomic transitions. M o r e o v e r , j5 and If have opposite

parity.
E l e c t r i c dipole t r a n s i t i o n s
Tj(ED) = (Pj • e) i s an odd o p e r a t o r .
<0f|T(ED)|^> = i ^ p M |0-е|^!>
D =e ^ rj {2jt и = и}
j
M a g n e t i c dipole and e l e c t r i c g u a d r u g o l e t r a n s i t i o n s
T
KMD + EQ> = i l i P j - Ï X I Î - ^ O + fttej-flîXcïïlipj.lXlî.r,)
= { ( ( P j X r p . f é x l ) )+ (e-ÎjXS-pj) + ( ï . ^ e . ? , ) }
T MD = j-g I ( [ J . + 2g . f 1 ' . {k1} (1) ) even operators
27гим({еШ (2) ) possible interferences

IAEA-SMR-12 / 2 1 47
9. E L E C T R I C DIPOLE RADIATIVE TRANSITIONS
9.1. Definitions
We c o n s i d e r a spontaneous t r a n s i t i o n between the two s t a t e s i and f

which have the e n e r g i e s Ef and Ef ( E ; > E f ) . We denote by a the wave v e c t o r ,
cr = |ст| i s the wave n u m b e r , и = ос/2-я = (Ej - E f ) / h is the f r e q u e n c y and e
is the p o l a r i z a t i o n v e c t o r of the single photon e m i t t e d in this t r a n s i t i o n .
If this t r a n s i t i o n is an e l e c t r i c dipole t r a n s i t i o n , the e m i s s i o n p r o b a b i l i t y
of s u c h a photon (per unit t i m e and within the i n f i n i t e s i m a l solid angle df2)
is given by
2
w(i,f)=^|<^|D£W|0f>|
where
L e t the i n i t i a l s t a t e be given by a' J' M' and s i m i l a r l y the final s t a t e by a J M .

Then we obtain
1 J
w(i,f)-=( ) <aj||Da>||a'J.>2±^î
\-M m M'/ ^
This f o r m u l a allows us to obtain the intensity d i s t r i b u t i o n when the a t o m

i n t e r a c t s with a s t a t i c f i e l d . S i m i l a r r e s u l t s hold f o r other m u l t i p o l e s .
U n l e s s the light s o u r c e is placed in a s t r o n g m a g n e t i c f i e l d , we do
not r e s o l v e the individual Z e e m a n components. We r a t h e r c o n s i d e r the
s u m of all components of a given line. If the a t o m s a r e not p o l a r i z e d
(i.e. if all s u b l e v e l s a r e equally populated) we can a v e r a g e over the i n i t i a l
s u b l e v e l s M' and s u m o v e r the f i n a l sublevels M. We also c o n s i d e r the
total p r o b a b i l i t y f o r a photon to be emitted in an a r b i t r a r y d i r e c t i o n with
a r b i t r a r y p o l a r i z a t i o n . P o r t h i s p u r p o s e we have to multiply by 8ir. The
new t r a n s i t i o n p r o b a b i l i t y is the E i n s t e i n c o e f f i c i e n t f o r spontaneous
e m i s s i o n A i f given by
A , <aj||D(1) ||o'J'>2
3 fi (2J'+1)
-M m M'/
M.M'
4 a3 1
Aif =
3 ^ i 7 .
w h e r e S ( a J , a ' J ' ) = < q<j||dW | | a ' J ' > is the line i n t e n s i t y of the t r a n s i t i o n .
In the d e s c r i p t i o n of r a d i a t i o n a b s o r p t i o n we often u s e the following
quantities:
48 FENEUILLE
Bfi = Ajf (Einstein coefficient for absorption)
/ №
ffi = &L A i f ^ ° f —J ( o s c i l l a t o r s t r e n g t h , a d i m e n s i o n l e s s quantity)
gj отг e \v/
L e t u s note that the E i n s t e i n c o e f f i c i e n t s f o r a b s o r p t i o n and induced

e m i s s i o n a r e , r e s p e c t i v e l y , r e l a t e d by:
g j Bfi = g j . Bif (Ej > Ef)

t t
A IE a'J1 aJ
R e g a r d l e s s w h e t h e r we d e s c r i b e a p r o c e s s in t e r m s of t h e E i n s t e i n
c o e f f i c i e n t o r t h e o s c i l l a t o r s t r e n g t h , a l l e x p l i c i t r e f e r e n c e to a t o m i c
s t r u c t u r e o c c u r s in t h e line i n t e n s i t y only (the f r e q u e n c y of the t r a n s i t i o n
i s u s u a l l y known f r o m e x p e r i m e n t ) .
In p r a c t i c e S i s c a l c u l a t e d in two s t e p s . F i r s t the r e d u c e d m a t r i x
e l e m e n t s a r e d e r i v e d f o r s o m e s i m p l e convenient coupling (usually LS).
T h i s m a t r i x i s then t r a n s f o r m e d into the e n e r g y s c h e m e (including s o m e -
t i m e s c o n f i g u r a t i o n i n t e r a c t i o n ) u s i n g the u n i t a r y t r a n s f o r m a t i o n <( a j | r j ) >
b e t w e e n t h e L S s t a t e s | r J M ) > and the e n e r g y e i g e n s t a t e s | a J M ) > . T h e
r e s u l t obtained r e a d s
S M ^ ' J ' ) ^ < o j | r J > < r j | | D ( D ||Г"J'> < Г ' J ' I a-'J' >
ГГ '
O b v i o u s l y , s u m m a t i o n m u s t be done b e f o r e s q u a r i n g ; t h e n i n t e r f e r e n c e o r
cancellation effects may appear.
9.2. The l i n e and m u l t i p l e t f a c t o r s
In LS coupling, the r e d u c e d m a t r i x e l e m e n t s of DW have the f o r m
< aSLjIlD*1' ||a'S'L'J'>
Since d № a c t s on o r b i t a l p a r t s only ( s p i n - i n d e p e n d e n t o p e r a t o r ) we can

write
rJ i j'l
< a S L j | | D t t > | | a ' S ' L ' J ' > = {[JltJ 1 ]} 1 / 2 6(S,S') \ \ (,-l)J + l + L4S
L' S L
X <aSL||DW ||a'S'L'>
The line f a c t o r á ? ( S L J , S'L 1 J ' ) i s defined by
J 1 J'
â t (SLJ, S ' L ' J ' ) = { [ j ] [ j ' ] } 1 / 2 6(S, S') • (-1 )J + 1 + L' + S
L' S L
IAEA-SMR-12 / 2 1 49
^ 2 ( S L J , S ' L ' J ' ) gives the r e l a t i v e i n t e n s i t i e s of the l i n e s of a m u l t i p l e t

in the c a s e of p u r e LS coupling. Since 6(S,S') a p p e a r s in we hence
obtain the s e l e c t i o n r u l e AS = 0. F r o m the p r o p e r t i e s of the 6j s y m b o l
we can d e r i v e a l s o the s e l e c t i o n r u l e s
ALI Š 1 S [L + L'J
A J I g 1 s [J + J ' l
The s u m m a t i o n p r o p e r t i e s of R a c a h ' s c o e f f i c i e n t s p r o v i d e u s with two

u s e f u l s u m r u l e s which r e a d
^Ts(SL'J',SLJ) = j g j | < a S L | | D « ||aSL'>|2

J
S ( S L ' J ' , S L J ) = [S]|< oSL||D ( 1 ) | | a S L ' > | 2

J.J"
We s e e that the r e d u c e d m a t r i x e l e m e n t | aSL | | d № | | a S L ' ^ | y i e l d s the
r e l a t i v e i n t e n s i t i e s of d i f f e r e n t m u l t i p l e t s . R e p e a t e d application of the
t e c h n i q u e s d e s c r i b e d in c h a p t e r s 4, 5, 6, m a k e s it p o s s i b l e to w r i t e t h i s
r e d u c e d m a t r i x e l e m e n t in a f i n a l f o r m , a s the p r o d u c t of a s i n g l e - e l e c t r o n
r e d u c e d m a t r i x e l e m e n t e 2 ^ n í || r W ||п'Л'^> which depends only on the
q u a n t u m n u m b e r s of the jumping e l e c t r o n and on a f a c t o r which we s h a l l
c a l l t h e m u l t i p l e t f a c t o r 9 t ( a SL, o ' S L ' )
< a S L | | D ( 1 ) H a' S' L 1 > = e 2 < n i || r ( 1 ) || n ' i 1 {a SL, a' SL')
where
< nil I rU) | | n ' i ' > = < n i | r | n ' i ' > = ( - l ) í _ í > nTí> < n i | r | n ' i ' >
With t h e s e definitions the line i n t e n s i t y with p u r e LS coupling i s given by
S ( a S L J , a ' S ' L ' J ' ) = ât2(SLJ, S L ' J ' ) á? 2 (a SL, a ' S L ' ) б (S, S' ) i > < n i | r | n ' i '> 2
Many a u t h o r s u s e a quantity a 2 defined by
2 = <ni|r|n'i'>2
" (4i2 - 1 )
The m u l t i p l e t f a c t o r d e p e n d s upon the two p a r t i c u l a r c o n f i g u r a t i o n s involved

in the t r a n s i t i o n . In any c a s e , it can be e a s i l y obtained by m e a n s of the
t e c h n i q u e s d e s c r i b e d in c h a p t e r s 4 , 5 , 6 . F o r e x a m p l e , if we c o n s i d e r
t r a n s i t i o n s of the type
iN oSL JM í N - l a Š L i ' S' L ' J ' M'
the m u l t i p l e t f a c t o r is given by:

50 FENEUILLE
iL 1 L"
1
N < âSL^^" aSL>j • {[L][L']} 1 / 2
( - i ) l + L + I + r
L je1 L SL
F r o m the f o r m u l a s obtained f o r the m u l t i p l e t f a c t o r s , it i s v e r y e a s y to

o b t a i n s u m r u l e s f o r line i n t e n s i t y . F o r t r a n s i t i o n s of, e . g . the type
- i N j T , we obtain:
^ S ( o S L J , o ' S L ' J ' ) = -Ц1 < n ' 4 ' || r U> || n " í " > 2 '
LT
L e t us r e m a r k t h a t the o s c i l l a t o r s t r e n g t h a l s o s a t i s f i e s s e v e r a l u s e f u l
s u m r u l e s . B e s t known i s the R e i c h e - T h o m a s - K u h n f - s u m r u l e , which
s t a t e s that t h e s u m of a l l o s c i l l a t o r s t r e n g t h s f r o m a given l e v e l n i s e q u a l
to the n u m b e r of e l e c t r o n s , the s u m going o v e r a c o m p l e t e s e t of s t a t e s n ' ,
including l e v e l s below n , above n , and continuum s t a t e s .
9.3. T r a n s i t i o n i n t e g r a l s
A s a l w a y s , the r a d i a l i n t e g r a l s a p p e a r i n g in t r a n s i t i o n p r o b a b i l i t i e s
a r e t h e q u a n t i t i e s which a r e m o s t d i f f i c u l t to o b t a i n . The a p p r o x i m a t i o n s
d e s c r i b e d in c h a p t e r 1 have b e e n u s e d , but the t a b l e s m o s t f r e q u e n t l y used
a r e t h o s e of B a t e s and D a m g a a r d ; t h e i r wave f u n c t i o n s a r e b a s e d on a
C o u l o m b a p p r o x i m a t i o n to the c e n t r a l f i e l d .
L e t us note that n i | r | n ' i 1 > is u s u a l l y m a x i m u m when |n - n' | i s
s m a l l e r t h a n ( Í - V ) and d e c r e a s e s r a p i d l y when | ( n - n ' ) | b e c o m e s g r e a t e r
t h a n 1.
In the h y d r o g e n i c a p p r o x i m a t i o n n í | r | n ' i ' )> b e h a v e s a s l / Z , so that f
b e h a v e s a s l / Z f o r t r a n s i t i o n s An = 0 and i s a c o n s t a n t f o r t r a n s i t i o n s Д п ^ О .
10. RELATIVISTIC E F F E C T S IN ATOMIC S P E C T R A
10.1. D i r a c equation
1 0 . 1 . 1 . D i r a c equation f o r a f r e e p a r t i c l e
E2 = ^ 2 с 4 + р 2 с 2
h 2 {ci Д - Э 2 } = м2 с 4 K l e i n - G o r d o n equation
h 2 с 2 д - h 2 a 2 - ц 2 с 4 = { - i R c ( o . v ) + m a t + /з^с 2 }
{ihc(a • V) +ih3t - jSmc2} = 0
г
c ( a . p ) +/3рс - E = 0
2
a® = , 3 = 1 , = 2S M U , [ a ß , ß ] + = 0
IAEA-SMR-12 / 2 1 51
I 0 0 <J
4X4 matrices
0 -I I a 0
1 0
а
0 1
=
0 -i
=
Il1 0
х= °y
0 1 1 0 i 0 Il 0 -1
Ф=
( E - / и с 2 ) ф 1 -с(ст-р)ф 2 = О
- c ( t j . p )фг + ( Е + Й С 2 ) Ф 2 = О
10.1.2. D i r a c equation f o r a p a r t i c l e i n t e r a c t i n g with a c l a s s i c a l field
E - E + eV р^тг = р + - А
h D = с ( a - n ) + ß ß d 2 - eV
(E -juc2 + ёЧ)фг - с(о-л)ф2 =0
-с(ст - 7 г 1 + (Е +|ис 2 + еУ)ф2 = 0
The n o n - r e l a t i v i s t i c l i m i t f o r p o s i t i v e e n e r g y s t a t e s i s obtained a s f o l l o w s :
c ( a - Ť ř ) « |uc 2 I eV I « ßc ф «ф
(ст-я)2-еу| = Wc^ W = (E - ßc 2 )
(ст-А)(ст-В) = ( Â - S ) + i(S-{ÂXB})
{ИХж} = - i ^ ( V X Â ) = -
+ (3 eV = Pauli
'^ " } Ration
52 FENEUILLE
10.2. E l e c t r o n in a c e n t r a l field
10.2.1. Motion c o n s t a n t s
h 0 = c{a-p)+ßpc2 - eU(r)
fi 1 = (r Xp)
[ h D , ~l] = - i c ( a X p )
(h D , a] = 2ic(3x p)
f =? +
[hD,j1 = 0
In t h i s way, it i s p o s s i b l e to obtain s t a t e s which a r e s i m u l t a n e o u s l y e i g e n -

f u n c t i o n s of h D , j*2, and j z .
10.2.2. G e n e r a l f o r m of s o l u t i o n s
N o n - r e l a t i v i s t i c l i m i t : Фг Фт <t>2~* ®
Without b e i n g i n c o n s i s t e n t , we can e x p e c t t h a t , in g e n e r a l ,
1
ф1 = ^ G ( r ) | | i j m >
where
||4jm> = < H , i m - i |jm> | i m - i > + 
( E + e U - M c 2 ) ^ \\t j m > -c(a-p)ф2 = 0
li-e j m > + (E + eU +дс 2 )ф 2 = 0
( a . V ) - | i i j m > = 2(-l) _ r +.
r dr 2r
I i j
X < 7 | | C ( 1 ) ||i> llüjm) [i = 2 j - i ]
1 i 1
2(-l)^ + { + i < ||C ( 1 ) | | i > < | | | s | | } > Г £ 3

f =1
U(je + l ) - i ( j e + l)] = ( - l ) i + M ( 2 j + l ) = 2k
IAEA-SMR-12/4,5 53
The s e c o n d equation i s s a t i s f i e d if we w r i t e
= -i ÍF(r)|ijíjm>
4 - G + - G = \ (E+MC 2 + e U ) F
dr r cn
Now it i s e a s y to show that
|iijm> = { i £ r - i } J | * i j m ;
so that
dF kF 1 ,_ о . „,
-5 — E - ц c z +eU G
dr r cti
Conclusion:
G
r |iijm>
k) =
. F
- i— |iljm>
r
dG 2ao
dr = |(l+€) + ° u} F
dF
= { ( 1 - е ) - SČlí u | G
dr - Î }
e = E/mc2
f ( F 2 + G 2 )dr = 1
о
10.2.3. N o n - r e l a t i v i s t i c l i m i t
A t t r a c t i v e potential: U = — S(r)
P o s i t i v e - e n e r g y s t a t e s ( d i s c r e t e + continuous)
e = 1 + a2e2 + a4 e4 +
G = G0 + a 2 G 2 +
F = AFJ + O 3 F 3 +
54 FENEUILLE
d 2 Gp Je<Jg + l) n ^
(W + eU)G 0 = 0
dr2
p = oaç, № + к
1
2 dr r
Negative-ejiejrj^y s t ä t e s J o n l ^ continuous)
e = - i + a 2 e2 + a 4 e 4 +
G = oG a + o 3 G 3 +
F = F 0 + a 2 Fz
10.2.4. C o u l o m b f i e l d
F o r t h i s s e c t i o n , s e e R e f . [ 1 1 ] , C h a p t e r V.
F o r bound p o s i t i v e e n e r g y s t a t e s we have
Z2 "Accidental" degeneracy
2
2n 2 e d e p e n d s on |/c] only
Z4 in 3
10.2.5. G e n e r a l f o r m of r a d i a l f u n c t i o n s
With a p o t e n t i a l s a t i s f y i n g the g e n e r a l conditions
S(0) = Z S(°o) = I
e a c h l e v e l can again be c h a r a c t e r i z e d by n ( i n t e g e r >0) i (integer < n) and

j (half i n t e g e r , Í ± i ) , but now the o n e - e l e c t r o n e n e r g i e s a r e no l o n g e r s i m p l y
r e l a t e d to n. H o w e v e r , n s t i l l h a s a p r e c i s e m e a n i n g , s i n c e it can be shown
t h a t (a) the n u m b e r of nodes of G (excluding the o r i g i n ) i s n - i - 1 and (b) the
n u m b e r of nodes of F (excluding the o r i g i n ) i s п - | к | . F u r t h e r m o r e we s e e
t h a t , if we e x c e p t the o r i g i n , the nodes of F and G cannot c o i n c i d e . Let us
m e n t i o n t h a t at the o r i g i n F / r and G / r d i v e r g e f o r j = | .
10.2.6. F u n d a m e n t a l m a t r i x e l e m e n t s
F r o m c e n t r a l - f i e l d o n e - e l e c t r o n s t a t e s , it i s p o s s i b l e to s t u d y the
e f f e c t s of v a r i o u s p e r t u r b i n g H a m i l t o n i a n s (Coulomb and B r e i t i n t e r a c t i o n
between electrons, Zeeman effect, hyperfine structure, radiative transitions,
e t c . ) , j u s t a s in the n o n - r e l a t i v i s t i c c a s e . All t h e s e i n t e r a c t i o n s can be
e x p r e s s e d in t e r m s of two t y p e s of o p e r a t o r s , n a m e l y ^
C® and {aC®}^
IAEA-SMR-12/4,5 55
P r o m the r e s u l t s d e r i v e d p r e v i o u s l y , we know t h a t the only p r o b l e m i s to

o b t a i n the c o r r e s p o n d i n g r e d u c e d m a t r i x e l e m e n t s .
F i r s t , it i s e a s y to show that
( n ' i ' j ' | | c ( k ) | | n i j ) = G ' G | | i j > + F ' F p j >
(n4"j||{aC< k >}( K > [I rue j ) = i F ' G ^ ' j ' H i a d ' C « } ^ » | | ^ >
- iG'F ||Í0.C1)C<K) }(К) р 3 > •
T h e n , it f o l l o w s i m m e d i a t e l y that
' j' k j 1 / V k Л \
( n ' i ' j 1 II C ( k ) Hnij) = G G ' l - l l ^ M l j l l j ' l W U 1 ] } 1
i i v J у 0 0 0
f j1 k j , / 7 . k 7 )
r+i 1
+ FF'(-l) {fjJIj'Hilli']) \
i Л' J \ о о 0 /
1
i2 2
i1
i' k Л
( n ' i ' j ' ||{aC ( k ) } ( K ) | | n i j > = i F ' G ( - l ) r { 3 [ j ] [ j ' ] [ K ] [ i ' ] [ i ] / 2 F i" i k
0 0 0
Li' j К
i2 ±г 1í
V к Л
• i G ' F ( - l ) { '{3 [j][j'] [К] [Í'] [í] / 2}^ i' I k
Уо о о
j' j к
H o w e v e r , the p r e c e d i n g f o r m u l a s can be w r i t t e n in a f o r m involving only
3j-symbols:
(n'i'j'||c<k> ||nij)= (-l)i + M 3 k 3

) l { l + ( - l ) k + í + í '}
\i 0 -\j
X A(k,í,i'){[j][j']}ž (GG'+FF1)
( n ' i ' j ' | | { a C ( k ) } ( K ) | | n i j ) = -i{[K][j][j']}* i { l + ( - l ) k + { + r+1

}
/ i k к \ /j- к j4
2Ц-1)1 [A (k, i i ) F ' G + A(k, Í i ) F G ' ]
\-l 0 1 / U -1 i
1 k К \ /j' К j \
+ (Л
- 1 )\Г + * [Д(к, i ' , Í ) G ' F - Д (k, í 1 , Í ) F ' G ]
56 FENEUILLE
Д ( а , Ь , с ) t r i a n g u l a r condition s y m b o l . The proof of t h e s e f o r m u l a s can

be c o n s i d e r e d a s an e x e r c i s e . L e t u s r e m a r k , h o w e v e r , that it i s e s s e n t i a l
to u s e the f o l l o w i n g identity:
= 2"* (-l)i + 1
[iH
10.3. F o u l d y - W o u t h u y s e n t r a n s f o r m a t i o n . Non-relativistic limit
F o r t h i s s e c t i o n s e e R e f . [9] . F o r an e l e c t r o n in a c e n t r a l field we have
H 2 _ Ho P4 . ft2 1 dV - ft2 A V
H H + ( f f i ) +
m - n r j
spin-orbit t e r m
10.4. B r e i t i n t e r a c t i o n , B r e i t - P a u l i a p p r o x i m a t i o n
F o r this section see Ref.Il] .
REFERENCES
[1] BETHE, H . A . , SALPETER, E. E . , Q u a n t u m M e c h a n i c s of O n e - a n d T w o - E l e c t r o n A t o m s , Springer

V e r l a g , Berlin ( 1 9 5 7 ) .
[2] C O N D O N , E . U . , SHORTLEY, G. H . , T h e T h e o r y of A t o m i c S p e c t r a , C a m b r i d g e U n i v e r s i t y Press ( 1 9 5 1 ) .
[3] SLATER, J . C . , Q u a n t u m T h e o r y of A t o m i c S t r u c t u r e , M c G r a w - H i l l , N e w York ( 1 9 6 0 ) .
[4] SHORE, B . W . , MENZEL, D . H . , P r i n c i p l e s of A t o m i c S p e c t r a , W i l e y , N e w York ( 1 9 6 8 ) .
[5] EDMONDS, A . R . , A n g u l a r M o m e n t u m i n Q u a n t u m M e c h a n i c s , P r i n c e t o n U n i v e r s i t y Press ( 1 9 6 0 ) .
[6] JUDD, B . R . , O p e r a t o r T e c h n i q u e s in A t o m i c S p e c t r o s c o p y , M c G r a w - H i l l , N e w York ( 1 9 6 3 ) .
[7] BRINK, D . M . , SATCHLER, G . R . , A n g u l a r M o m e n t u m , C l a r e n d o n Press, O x f o r d (1968).
[8] JUDD, B. R . , S e c o n d Q u a n t i z a t i o n a n d A t o m i c S p e c t r o s c o p y , T h e John H o p k i n s Press, B a l t i m o r e ( 1 9 6 7 ) .
[9] MESSIAH, A . , Q u a n t u m M e c h a n i c s , D u n o d , Paris ( 1 9 6 4 ) .
[10] HEITLER, W . , T h e Q u a n t u m T h e o r y of Radiation, O x f o r d U n i v e r s i t y Press ( 1 9 4 4 ) .
[11] ROSE, M . E . , R e l a t i v i s t i c E l e c t r o n T h e o r y . W i l e y , N e w York ( 1 9 6 1 ) .
IAEA-SMR-12/52
THEORY OF ATOMIC STRUCTURES,

TRANSITIONS, AND M O L E C U L A R P O T E N T I A L
CURVES WITH E L E C T R O N CORRELATION
IN GROUND AND E X C I T E D S T A T E S
O. SIN AN OG LU
Sterling Chemistry Laboratory,
Yale University, New Haven, Conn.,
United States of America
and
Kuramsal Kimya Bölümü
Orta Dogu Teknik Evrenkenti,
Ankara, Turkey
Abstract
THEORY OF A T O M I C STRUCTURES, T R A N S I T I O N S , AND MOLECULAR POTENTIAL CURVES WITH

ELECTRON CORRELATION IN GROUND AND EXCITED S T A T E S .
1. Introduction; 2, N e w a t o m i c - s t r u c t u r e t h e o r y with e l e c t r o n c o r r e l a t i o n ; 3 . T h e o r y of t h e N - e l e c t r o n
excited state; 4 . T h e a l l - e x t e r n a l c o r r e l a t i o n E^ and e n e r g y l e v e l s ; 5. T r a n s i t i o n p r o b a b i l i t i e s ;
6. M o l e c u l a r b i n d i n g and p o t e n t i a l e n e r g y c u r v e s ; 7. T h e s e m i - i n t e r n a l c o r r e l a t i o n e f f e c t and m o l e c u l a r
potential energy curves; 8 . T h e c h a r g e w a v e f u n c t i o n and c h a r g e d i s t r i b u t i o n r e l a t e d p r o p e r t i e s of m o l e c u l a r
excited states.
1. INTRODUCTION
M o d e r n a t o m i c and m o l e c u l a r e l e c t r o n i c s t r u c t u r e t h e o r y can be
s u b d i v i d e d i n t o t h r e e p a r t s : (1) o r b i t a l t h e o r y , (2) c o r r e l a t i o n t h e o r y ,
a n d (3) r e l a t i v i s t i c t h e o r y .
T r a d i t i o n a l m e t h o d s , t h e H a r t r e e - F o c k (H. F . ) m e t h o d , h y d r o g e n i c
Z - d e p e n d e n t m e t h o d , the C o n d o n - S h o r t l e y and S l a t e r - R a c a h m e t h o d s , the
m o l e c u l a r o r b i t a l (M. O. ) a n d v a l e n c e bond ( V . B . ) m e t h o d s a r e a l l b a s e d
on t h e o r b i t a l a p p r o a c h .
Y e t , m a n y a t o m i c a n d m o l e c u l a r p r o p e r t i e s a r e not given a d e q u a t e l y ,
n o r at t i m e s even qualitatively c o r r e c t l y by o r b i t a l s . Table I shows this.
M o l e c u l a r binding, v a n - d e r - W a a l s a t t r a c t i o n s , and e l e c t r o n a f f i n i t i e s
r a r e l y e x i s t e v e n if one u s e s t h e b e s t o r b i t a l s , t h e H. F . o n e s . T r a n s i t i o n
p r o b a b i l i t i e s c a n b e i n c o r r e c t b y f a c t o r s l i k e 2 - 3 in C , N, O, . . . , a n d
f a c t o r s l i k e 1 0 - 3 0 in M g , Si, C l , F e , e t c . T h e d i f f i c u l t y in t h e s e p r o p e r t i e s
i s d u e t o " e l e c t r o n c o r r e l a t i o n " , t h e d e v i a t i o n of t h e m o t i o n s of e l e c t r o n s
f r o m t h e i r a v e r a g e o r b i t a l b e h a v i o u r due t o i n s t a n t a n e o u s C o u l o m b r e p u l s i o n s .
T h e a t o m i c and m o l e c u l a r N - b o d y p r o b l e m , t h e m a n y - e l e c t r o n p r o b l e m ,
d i f f e r s in i t s n a t u r e f r o m t h e " m a n y - b o d y p h y s i c s " p r o b l e m s l i k e e l e c t r o n
gas, n u c l e a r m a t t e r , superconductivity, field theory, etc. F o r this
g r e a t d i f f e r e n c e a n d c o m p a r i s o n of v a r i o u s p r o b l e m s a s w e l l a s h i s t o r i c a l
a p p r o a c h e s to e l e c t r o n c o r r e l a t i o n , p l e a s e s e e t h e b o o k b y O. S i n a n o g l u
a n d K . A. B r u e c k n e r , " T h r e e A p p r o a c h e s t o E l e c t r o n C o r r e l a t i o n in
A t o m s " ( Y a l e Univ. P r e s s , 1971). T h e b o o k a l s o g i v e s t h r e e m o d e r n
57
58 SINANOGLU
T A B L E I. O R B I T A L THEORY VERSUS E X P E R I M E N T - I M P O R T A N C E
OF E L E C T R O N C O R R E L A T I O N IN ATOMIC AND M O L E C U L A R
PROPERTIES
Orbital theory Experiment

Property
(Hartree-Fock; MO) (Hartree-Fock + correlation)
E l e c t r o n a f f i n i t y of -0.54 " 1.465

o x y g e n a t o m (eV)
D e of F 2 m o l e c u l e (eV) - 1 . 37 c
1. (
e
U of H e . . . H e P. E. c u r v e van-der-Waals van-der-Waals
repulsion attraction
( m i n i m u m u / к ~ 10 К . )
Excited s t a t e energy
separation-term splitting
Ratio — i n 1s2 2 f ? of 0 + 4 1.47 ' 3.15
Electric dipole transition-

o s c i l l a t o r s t r e n g t h f g ^ of
Is 2 2s? 2p 2 (3 P) Is 2 2s2p 3 (3 D) of N + 0. 236 8 0.101
O s c i l l a t o r s t r e n g t h f E 1 of P +
3p2(3P)-»3p3(3P°) 0. 2 5 6 J
a
R O O T H A A N , C . C . I . , KELLY, P . S . , Phys. Rev. 131, (1963) 1 1 7 7 .
b
BATES, D. R . , MOISEWITSCH, B. L. , P r o c . Phys. S o c . (London) A 6 8 , (1955) 5 4 0 .
c
WAHL, A . C . , J. C h e m . Phys. 4 1 , (1964) 2 6 0 0 . N o t e o p p o s i t e sign t o e x p e r i m e n t a l .
d
I C Z K O W S K I , R. , MARGRAVE, J. , J. C h e m . Phys. 30, ( 1 9 5 9 ) 4 0 3 . (Zero point correction from
GAYDON, A . G . , Dissoc. E n e r g i e s C h a p m a n H a l l L t d . , London ( 1953).
e
KESTNER, N . R . . SINANOGLU, O . , J. C h e m . Phys. 4 5 , ( 1 9 6 6 ) 194.
' Based on MOORE, C . , A t o m i c Energy L e v e l s , NBS, W a s h i n g t o n D. C . ( 1 9 4 9 ) .
a
8 Calculated from the Hartree-Fock wave functions (cf. ).
h HEROUX, L. , Phys. Rev. 153, ( 1 9 6 7 ) 1 5 6 .
' BECK, D . R . , SINANOGLU, O. , Phys. Rev. Lett. 28, (1972) 9 4 5 .
J
SAVAGE, B . D . , LAURENCE, G . M . , Astrophys. J. 146, ( 1 9 6 6 ) 940.
a p p r o a c h e s to e l e c t r o n c o r r e l a t i o n in g r o u n d - s t a t e a t o m s . F o r excited
s t a t e s , t h e t h e o r y of e l e c t r o n c o r r e l a t i o n h a s b e e n d e v e l o p e d r e c e n t l y by
Sinano§lu ( N o n - C l o s e d Shell M a n y - E l e c t r o n A t o m i c S t r u c t u r e T h e o r y
N C M E T / M E T ) [1] and applied and c o m p a r e d with e x p e r i m e n t s by h i m and
his co-workers.
T h e t h i r d p h a s e of e l e c t r o n i c s t r u c t u r e t h e o r y , the r e l a t i v i s t i c one,
b e c o m e s p a r t i c u l a r l y c r u c i a l at a t o m s like tin (Sn) and h i g h e r Z - v a l u e s .
R e l a t i v i s t i c H . F . o r b i t a l s a r e obtained in s e v e r a l l a b o r a t o r i e s , but the
b a s i c t h e o r y i n v o l v e s c o r r e l a t i o n , r e l a t i v i s t i c and r a d i a t i v e e f f e c t s beyond
t h e D i r a c - l i k e o r b i t a l s and is v e r y l i t t l e developed at p r e s e n t .
In t h i s p a p e r we f i r s t outline t h e new e l e c t r o n i c s t r u c t u r e t h e o r y
with e l e c t r o n c o r r e l a t i o n in ground and excited s t a t e s ( N C M E T / M E T ) [1].
IAEA - S M R - 1 2 / 5 2 59
T h e n we a p p l y it to o p t i c a l t r a n s i t i o n p r o b a b i l i t i e s c o m p a r i n g the r e s u l t s
with new e x p e r i m e n t a l a t o m i c m e t h o d s . T h e new t h e o r y b r i n g s t h e
a c c u r a c y [2, 3] to 5-10% c o m p a r e d to f a c t o r s of 2 - 3 0 of the e a r l i e r m e t h o d s .
T h e m o l e c u l a r - p o t e n t i a l - e n e r g y - c u r v e s p r o b l e m i s a l s o one of highly
o p e n - s h e l l s with c r u c i a l c o r r e l a t i o n e f f e c t s l e a v i n g the MO 1 s i n a d e q u a t e [4].
T h e N o n - C l o s e d Shell M a n y - E l e c t r o n T h e o r y (NCMET) now p e r m i t s a
s y s t e m a t i c t r e a t m e n t of t h e s e c o r r e l a t i o n e f f e c t s a l s o . T h u s it h a s b e c o m e
p o s s i b l e with the u s e of N C M E T to obtain p o t e n t i a l e n e r g y c u r v e s and
s u r f a c e s h a v i n g a p p l i c a t i o n s in a t o m and m o l e c u l e c o l l i s i o n p r o b l e m s , in
m o l e c u l a r s p e c t r o s c o p y and in c h e m i c a l k i n e t i c s [5].
2. NEW A T O M I C - S T R U C T U R E T H E O R Y WITH E L E C T R O N
CORRELATION
T h e a t o m i c s t r u c t u r e t h e o r y m a y be t r e a t e d in two p a r t s :
(1) ground s t a t e s , (2) e x c i t e d s t a t e s . M o r e r i g o r o u s l y t h i s d i v i s i o n i s
one into (a) c l o s e d (and q u a s i - c l o s e d s h e l l s , i. e. s i n g l e d e t e r m i n a n t a l
s t a t e s ) and (b) open s h e l l s y s t e m s .
L e t u s c o n s i d e r f i r s t the t h e o r y of the g r o u n d s t a t e s . T h e g e n e r a l
n o n - r e l a t i v i s t i c H a m i l t o n i a n can b e w r i t t e n a s
IN IN
H (i)
w h e r e the t e r m s h? a r e o n e - e l e c t r o n o p e r a t o r s
hN-H-Ц
i
and the t w o - e l e c t r o n o p e r a t o r i s the i n t e r e l e c t r o n i c C o u l o m b r e p u l s i o n
Sij = 7 ~ (3)
ij
T h e H a r t r e e - F o c k f u n c t i o n of such a s y s t e m i s
^RHF = ^ ( 1 , 2 , 3, . . . i, . . N) (4)
with i = i(xi ) a s p i n - o r b i t a l with an a s s o c i a t e d e n e r g y E R H F .

C o m p a r i n g with the e x a c t solution of (1)
HI// = ENRI// ( E n r = non-relativistic energy) (5)
we d e f i n e t h e c o r r e l a t i o n e n e r g y a s
E E + E
NR " RHF CORR (6)
60 SINANOGLU
T h e a t o m i c Í^RHP i m p l i e s the 0(3) © SU(2) s y m m e t r y f o r e a c h s p i n -

o r b i t a l ; i. e. c e n t r a l s y m m e t r y in c o n f i g u r a t i o n s p a c e and s p i n f o r e a c h
spin-orbital. H e r e the designation " R H F " m e a n s " r e s t r i c t e d H a r t r e e -
F o c k " . T h i s i s t h e s t a n d a r d H a r t r e e - F o c k m e t h o d u s e d in e x c i t e d s t a t e s .
O u r p r o b l e m i s to o b t a i n t h e r e s t of t h e e x a c t w a v e f u n c t i o n (wf)
a n d E c o r r f o r t h e g e n e r a l N - e l e c t r o n (N - e") p r o b l e m . We h a v e the N -
fermion Hilbert space . . . ® L 2 . F i r s t we d e f i n e t h e o r t h o g o n a l
c o m p l e m e n t of $ R H F = ф0:
ф = ф0+ x With < ф01 X > = 0 (7)
<ф0|ф0>=1 and = 1+ < x | x > (8)
s o a s to k e e p t h e c o r r e l a t i o n wf o r t h o g o n a l t o the H . F . s e a , a s in E q . (7).
T o h a v e a n e s t i m a t e of c o r r e l a t i o n we h a v e
< 2 ^ « l a n d | « 2 £ $ 1 % (9)
1
ERHF
We h a v e t h e a d v a n t a g e o v e r a n i n f i n i t e s y s t e m l i k e a n e " - g a s t h a t < x | x У
i s finite, but the finite N-e" p r o b l e m h a s other difficulties a s c o m p a r e d to
an infinite s y s t e m .
W e s h a l l u s e t h e t w o t o o l s w e h a v e i n t r o d u c e d f o r t h e f i n i t e N-body-
problem:
(1) T h e m e t h o d of s u c c e s s i v e p a r t i a l o r t h o g o n a l i z a t i o n s M S P O
( s u c c e s s i v e d e c o m p o s i t i o n s of t h e N - p a r t i c l e H i l b e r t s p a c e ) [6] and
(2) T h e s u b v a r i a t i o n a l p r i n c i p l e s (we a l s o c a l l e d it t h e v a r i e d - p o r t i o n s
a p p r o a c h V P A [1] ).
T o u s e M S P O f o r a g r o u n d s t a t e we s t a r t with i£ r h f = Д ( s i n g l e S l a t e r
d e t e r m i n a n t ) . Suppose f o r the m o m e n t we have the exact wave function
фЫ1,х2, . . . xn).
W e m a k e t h e wf s u c c e s s i v e l y o r t h o g o n a l t o N , t h e n t o ( N - l ) s p i n -
o r b i t a l p r o d u c t s down t o one s p i n - o r b i t a l l e f t , b y S c h m i d t o r t h o g o n a l i z a t i o n
p r o c e d u r e s , and f i n a l l y we s u m a l l the n u m b e r s t h u s c o n s t r u c t e d .
s o
X = - |ф 0 > <<í>ok > > =0 <10)
and
(И)
N o t e t h a t x i s in t h e N - e l e c t r o n s p a c e , but b e c a u s e of t h e s p i n - o r b i t a l in
t h e d e n o m i n a t o r it i s m u l t i p l i e d b y an ( N - l ) - e l e c t r o n f u n c t i o n
[1, 2, . . . , h , k , . . . N } and s o (11) d e f i n e s a ( 1 - e " ) - f u n c t i o n ; a l s o n o t e t h a t
f j (x ; ) d e p e n d s on i.
W e d e f i n e x1 a s :
X1 = x - У Л*Ч|1,2 h , k , . . . N > < 1 , 2 , . . , h , k , . . ,N|X >} (12)
i = 1
IAEA - S M R - 1 2 / 5 2 61
We t h e n do t h e s a m e in t h e ( N - 2 ) - e l e c t r o n s p a c e , e t c . We c a l l t h e (N-2)
m e m b e r û | j , t h e (N-3) - o n e t h e t h e ûj'jk , . . . and f i n a l l y s u m t h e m a l l up
and obtain
N N N
{ Û } + {Û + +
ф = Ф0 + Y Ф + X b i 'iik> • • • <Û123...N> ( 1 3
>
i=1 i>j ijk
with e. g.
{u
ij}= W (14)
and we obtain f r o m E q s (10)-(12) a l s o the " o r b i t a l - o r t h o g o n a l i t y " r i g o r o u s l y .
< ф > =0, Kûyfxi, x - í U í x j ) ) =0, etc. (15)

x
i
with £ = 1, 2, . . . N. T h e s e c o n d p a r e n t e s e s contain a f u n c t i o n of Xj b e c a u s e
we only i n t e g r a t e with r e s p e c t to x j , and s o on. T h i s i s r e l a t e d to the F o c k -
Dirac density p = £ | - O 0 | .
T a k e и^ к е , f o r e x a m p l e . It can be put a s a s u m of a l l p o s s i b l e p r o d u c t s
of p r e v i o u s û ' s without r e p e a t e d s u b s c r i p t s .
f
û'ijki = fj 4 e ) + tfk û
ij ) + u
ijk ) + ( û
û û
kf) + - - . + úijkř (16)
T h e l a s t t e r m i s a q u a t e r n a r y " c o l l i s i o n " of t h e type J | a g a i n s t b i n a r y

c o l l i s i o n s like о о', e t c .
Not only i s (16) a f i n i t e c l o s e d e x p r e s s i o n but it a l s o i n t r o d u c e s a
c l o s e d e x p r e s s i o n f o r the e n e r g y , u s i n g E q s (13-16) in
E — - — j — = E (17)
/
T h e next s t e p is t o v a r y a l l c o m p o n e n t s
{ó^} = {ófj, áújj ÔÛm_ _N} (18)
o b t a i n i n g a f i n i t e n u m b e r of coupled E u l e r e q u a t i o n s that a r e e q u i v a l e n t
to S c h r ö d i n g e r 1 s equation. B u t t h e detailed e n e r g y now gives i n s i g h t into
t h e c o n s t i t u e n t s of ? and E and we can p r o c e e d to g u e s s o r d e d u c e the
i m p o r t a n t p a r t s and only v a r y t h o s e .
We c h o o s e a s i g n i f i c a n t p o r t i o n of the Ë and v a r y it. We have an
E u l e r ( n o n - h o m o g e n e o u s ) e q u a t i o n whose solution m a y e x i s t . If not, it
c o m e s f r o m a w r o n g c h o i c e of the i m p o r t a n t p o r t i o n of Ë and it i s
r e c o g n i z e d b e c a u s e if the s o l u t i o n e x i s t s we get s t a t i o n a r y p o r t i o n s of Ë .
6 ('important part') =0 (19)

62 SINAN OG LU
W e s h a l l p r o c e e d t o show t h a t t h e ûjj a r e t h e m o s t r e l e v a n t t e r m s . So
f r o m t h e E u l e r e q u a t i o n s we get t h e ûjj ' s . H o w e v e r , we h a v e l o s t the
u p p e r bound p r o p e r t y
E ф (important part) (20)
B u t we can u s e t h e ûjj o b t a i n e d and o b t a i n f r o m t h e f u l l Ë of E q . (17):
E = (Imp. ) + R' (21)
and a m e a s u r e of a d e q u a c y of t h e c h o i c e i s t h e s m a l l n e s s of R ' . One can

e v e n o b t a i n the l o w e r b o u n d s f r o m t h i s m e t h o d . W e can a l s o p r o c e e d in
t h e s a m e w a y f u r t h e r and o b t a i n h i g h e r a p p r o x i m a t i o n s [7].
Lately MSPO h a s been developed f o r the density m a t r i x o p e r a t o r
D = |^>0| (22)
a l s o with D = D r h f + D x b y 0. Sinanoglu and T . Shibuya (J. M a t h . P h y s .

1_0, 1032).
F r o m t h e M S P O and the s u b v a r i a t i o n a l a p p r o a c h d i s c u s s e d a b o v e we
c a n d e r i v e m a n y a p p r o x i m a t i o n s and t h e o r i e s , but f o r a t o m s t h e - m o s t
a p p r o p r i a t e one e m e r g e s f r o m p h y s i c a l c o n s i d e r a t i o n s . We c a l l it the
" M a n y - e l e c t r o n t h e o r y of a t o m s and m o l e c u l e s f o r g r o u n d s t a t e s " ( M E T ) [ l , 7].
In c l o s e d - s h e l l s y s t e m s , we showed t h a t ( 1 - е " ) - f u n c t i o n s a r e v e r y
s m a l l [7]
fi « 0 (23)
f o r i n s t a n c e f o r H e , t h e f c o n t r i b u t e r o u g h l y 0.001 eV to the e n e r g y w h i l e
t h e t o t a l c o r r e l a t i o n e n e r g y i s 1.1 eV. Why a r e t h e û j ^ , û£j-ki f o r t r u e
3, 4 - b o d y c o l l i s i o n s s m a l l ? We a r e d e a l i n g with H . F . e " ' s . T h e s e h a v e
i n d i v i d u a l and d i s t i n c t o r b i t a l m o t i o n s . T h e y i n t e r a c t t h r o u g h a v e r a g e d
H . F . potentials
Si (xj )
The difference to the instantaneous Coulomb repulsions is

N
mii =
Hex-HHF- X I 77- - š ; ( j ) - š : ( i ) + J ^ (24)
i>j ü
T h e m j j i s t h e " f l u c t u a t i o n p o t e n t i a l " [1] given by the d i f f e r e n c e b e t w e e n
t h e C o u l o m b p o t e n t i a l (long r a n g e , i n f i n i t e f o r v a n i s h i n g r t j ) and t h e H . F .
p o t e n t i a l ( f i n i t e a t r ^ -» 0, b u t a l s o l o n g r a n g e ) w h i c h t a k e s the l o n g r a n g e
p a r t q u i t e w e l l i n t o a c c o u n t . So m ^ i s of q u i t e s h o r t r a n g e ( h a s even a
m i n i m u m in it s o m e t i m e s ) . I t s r a n g e i s s m a l l e r t h a n a F e r m i h o l e
a C O R R < a F . S o f o r t h r e e e^ t h e w o r s t p o s s i b i l i t y i s , a t m o s t , two s p i n s t h e s a m e .
IAEA - S M R - 1 2 / 5 2 63
äcORR
and {ûjj} and t h e i r p r o d u c t s d o m i n a t e

N
^MET = W + ^ ÎÛij> + i Û
û X Û
k«> + {U X U X U } +
(25)
> <j
with i , j =£{k,1}.
The variational MET energy [1,7] is
E S E = Erhf + ; ^ + R- (26)
with ë _ 2< j ^ ( i j ) I gjj I ûjj > + < ûjj )ej + ej + mjj ] u.j >
Û
+ < ij IÛy >
where
е-i 11
1 - е- (27)
E q u a t i o n (27) i s called a " H e - l i k e e q u a t i o n " , b e c a u s e i t l o o k s j u s t like

the H e - a t o m e q u a t i o n . F o r a ( m a n y - e " ) - s y s t e m we have two e x t r a e f f e c t s .
F i r s t , t h e " H . F . s e a " m o d i f i e s the ûjj through change of t h e o r b i t a l and the
total H.F. potential. The second effect comes f r o m the " o r b i t a l orthogonality",
<Ûy \l )xi = 0, of Eq.(15) b e c a u s e the e" cannot go to occupied Orbitals,
T h i s i s the " e x c l u s i o n e f f e c t " and c a n even l e a d to " e x c l u s i o n binding" in
molecules.
F o r the He a t o m t h e c o m p l e t e c o r r e l a t i o n e^ h a s a s an u p p e r bound
(28)
only in t h e ground s t a t e but it i s m o r e t r o u b l e s o m e f o r excited s t a t e s .

C o m p a r e d to t h e s e H e - s t a t e s , the p a i r s of the ( N - e " ) - s y s t e m a r e s i m p l e r
to t r e a t . H e r e E q . (28) a p p l i e s to a l l the p a i r s of the a t o m ! T h i s i s
p o s s i b l e b e c a u s e of E q . (15).
T h e q u e s t i o n i s w h e t h e r t h e r e e x i s t s a p r o h i b i t i v e l y l a r g e n u m b e r of
p a i r s . A c t u a l l y the s y m m e t r y r e d u c e s the n u m b e r of d i s t i n c t p a i r s , f o r
i n s t a n c e e (2px2) = e (2py2). So", i n s t e a d of having p a i r s of the o r d e r of
N ( N - l ) / 2 , we h a v e ~ N . T h i s p r o b l e m is a l m o s t a s s i m p l e a s the H . F .
m e t h o d . It i s m u c h e a s i e r t h a n the o r d i n a r y slowly c o n v e r g e n t t o t a l С. I.
(configuration interaction).
64 SINAN OG LU
In a p p l y i n g the M E T e q u a t i o n s one m u s t r e c a l l that E £ E H F + £ ?..

i J
even though E q . (28) h o l d s f o r e a c h (ij). T o get an u p p e r bound to E , one
n e e d s the e x t r a m a t r i x e l e m e n t s like
<û123|m13|Û32l> =
(and t h e r e a r e r e p e a t e d s u b s c r i p t s s o you a r e including h i g h e r c o r r e l a t i o n

t e r m s ) which a r e in the R' of
и
E S E
RHF + + R' (26)'
i>j
To e s t i m a t e R' is h a r d w o r k . I n d i r e c t l y you can show that R 1 is

e x p e c t e d to b e s m a l l . (The exactly soluble a t o m m o d e l of M . M o s h i n s k y [8]
h a s b e e n u s e d r e c e n t l y to a n a l y s e such e f f e c t s [9]. M a n y r e c e n t c a l c u l a t i o n s
u s i n g M E T a l s o show R' to be s m a l l a s p r e d i c t e d b y the t h e o r y . )
E a c h ejj b e h a v e s d i f f e r e n t l y , so old r u l e s like
(1) large correlation

pre-MET rules-of-
(2) e small correlation t u m b which M E T
showed to be i n c o r r e c t
(3) e e,,. - 1 eV
do not apply.
New r u l e s p r e d i c t e d by t h e new t h e o r y which t u r n e d out to be c o r r e c t a r e :
(1) All a r e n e e d e d , in f a c t e , and
(2) T h e r e a r e two t y p e s of the individual p a i r c o r r e l a t i o n s :

T h e r e a r e " H e - l i k e p a i r s " ; we c a l l t h e s e e^ , " d y n a m i c a l p a i r s " .
T h e y depend on s h o r t - r a n g e l o c a l e f f e c t s which e x p l a i n s why C . I . d o e s not
w o r k and it i s b e t t e r to u s e the H y l l e r a s - t y p e c o r r e l a t i o n f o r t h e m
ûjj ( r 1 2 o r r> , r<)
Our " e x c l u s i o n e f f e c t " i s s m a l l on such p a i r s and s o i s the " H . F . s e a "

p o t e n t i a l change e f f e c t . If you have such a p a i r you can t r a n s f e r i t s
€jj - v a l u e quite w e l l to d i f f e r e n t ions, a t o m s o r m o l e c u l e s . T h a t i s to s a y
dynamical pairs are transferable.
But in e x c i t e d s t a t e s and ground s t a t e s that a r e not r e a l l y c l o s e d s h e l l s
t h e r e a r e a l s o n o n - t r a n s f e r a b l e p a i r s . In t h i s c a s e we s p e a k of " n o n -
dynamical pairs". F o r e x a m p l e the (2s 2 ) p a i r in n e u t r a l neon and i t s i o n s
differs greatly.
IAEA - S M R - 1 2 / 5 2 65
In neon lü?2£?2p 6 , e(2s 2 ) N e œ °> but in t h e ion Ne + 6 , l s 2 2 s 2 , e(2s 2 ) N e + 6

« - 3 . 5 eV. T h i s c o m e s f r o m the " e x c l u s i o n e f f e c t " . F o r t u n a t e l y n o n -
t r a n s f e r a b l e p a i r s a r e s i m p l e to c a l c u l a t e .
T h e r e a r e t h r e e a p p r o a c h e s f o r closed s h e l l s : M E T , the d i a g r a m m a t i c
p e r t u r b a t i o n t e c h n i q u e [10] and t h e n o n - u n i f o r m e l e c t r o n g a s t r e a t m e n t [11]
w h i c h , h o w e v e r , d i v e r g e s . M E T p e r m i t s p h y s i c a l insight into the c o r r e -
l a t i o n m e t h o d s it i n t r o d u c e s . T h e d i a g r a m m e t h o d d o e s not p r e d i c t t h e
e f f e c t s a s M E T , but i s a t e c h n i q u e .
F o r g e n e r a l e x c i t e d s t a t e s we h a v e at p r e s e n t only one m e t h o d , the
n o n - c l o s e d s h e l l M E T , the NC M E T [1]. T h e d i a g r a m m a t i c t e c h n i q u e d o e s
not apply to s u c h s y s t e m s .
3. T H E O R Y OF T H E N - E L E C T R O N E X C I T E D STATE
Above we a n a l y s e d the ( N - e " ) - g r o u n d - s t a t e p r o b l e m u s i n g two g e n e r a l

t o o l s we d e v i s e d f o r the p u r p o s e .
(a) MPSO: S e p a r a t i n g the L 2 ® L 2 ® . . . <2> L 2 H i l b e r t s p a c e we pick
up a f i n i t e p a r t of the infinite H i l b e r t s p a c e . We s t a r t with t h e H . F . s e t
of occupied s p i n - o r b i t a l s (s. o. ' s ) .
It i s a s if f o r e a c h s. o. you find an i m a g e outside t h e H . F . s e a , then
f o r e l e c t r o n p a i r s , t r i p l e t s , e t c . , until you h a v e c o v e r e d t h e whole s e t a s
shown in the f i g u r e
© f.
N
but t h i s i s only a f o r m a l solution; then we n e e d a m e t h o d f o r a p p r o x i m a t i o n s

and c a l c u l a t i o n s , so we h a v e :
(b) the " s u b v a r i a t i o n a l p r i n c i p l e " : P i c k i n g out the m o s t r e l e v a n t
p o s i t i o n of the E , c h e c k i n g if it l e a d s to s t a t i o n a r y s o l u t i o n s and then getting
an u p p e r bound u s i n g the f u l l v a r i a t i o n a l e x p r e s s i o n .
U s i n g t h e s e t o o l s and p h y s i c a l n o t i o n s , we obtained E q . (2 5). F r o m
t h i s we d e r i v e d o u r decoupled p a i r c o r r e l a t i o n s in the e n e r g y
(29)
i>j
with
N
(30)
i>j
t h i s w a s a new p r e d i c t i o n of t h e t h e o r y by the a u t h o r (1959). F o r the
e " - g a s t h e o r y which m a n y w o r k e r s (Slater and o t h e r s ) t r i e d to apply to
a t o m s , E q . (30) i s not t r u e .
66 SINANOGLU
Without R 1 we h a v e no u p p e r bound to E . H o w e v e r , f o r each " H e - l i k e

equation" we h a v e an u p p e r bound to i t s p a i r e n e r g y
сц (Йц) (31)
E q u a t i o n s (29-31) a r e not u s e d in n u c l e a r t h e o r y . In n u c l e a r t h e o r i e s a l l
û ' s depend on a l l o t h e r û ' s . (cf. E . U . Condon, Rev. Mod. P h y s .
(1968) 872).
We h a v e two t y p e s of е ц , d y n a m i c a l ( t r a n s f e r a b l e p a i r s ) and a l s o n o n -
d y n a m i c a l . E x a m p l e s of the f i r s t type a r e I s 2 and 2p 2 ; of the s e c o n d type
2 s 2 , which i s n o n - t r a n s f e r a b l e but e a s i e r to c a l c u l a t e .
G e n e r a l N - e l e c t r o n n o n - c l o s e d s h e l l s (excited s t a t e s )
T h e c l o s e d - s h e l l t h e o r y w a s i n t r o d u c e d by the a u t h o r and developed

b e t w e e n 1959 and 1964 [7] in o u r l a b o r a t o r y ; i t s a p p l i c a t i o n s a r e studied
and continued in s e v e r a l o t h e r l a b o r a t o r i e s . T h e n o n - c l o s e d s h e l l M E T ,
N C M E T [1] w a s obtained and applied b e t w e e n 1964 and 1970 by t h e a u t h o r
and h i s c o - w o r k e r s . It led to an a t o m i c - s t r u c t u r e t h e o r y [1-3] capable of
a c c u r a t e p r e d i c t i o n s of m a n y p r o p e r t i e s l i k e t r a n s i t i o n p r o b a b i l i t i e s ,
h y p e r f i n e s t r u c t u r e , e t c . ; it i s in good a g r e e m e n t with new e x p e r i m e n t s
c a r r i e d out in 1968 and l a t e r .
We c a n now u s e the n o n - c l o s e d - s h e l l t h e o r y even f o r ground s t a t e s ,
b e c a u s e it g i v e s m o r e i n f o r m a t i o n .
C o n s i d e r f o r i n s t a n c e c a r b o n I.
0RHF (ground s t a t e of C) = ( l s 2 2 s 2 2 p o 2 p " ) c a r b o n 3

P
T h e Roothaan H . F . m e t h o d (1960) is u s e d . In g e n e r a l
J с л
RHF = к к (32)
K=1
with the CR d e t e r m i n e d by s y m m e t r y . F o r n e u t r a l c a r b o n , f o r the
ls 9 '2s 2 2p 2 1 S s t a t e we h a v e к = 3
фт1, = ^ [ 1 s 2 2 s 2 (2p2 + 2py + 2p 2 )]
we need t h e s e t h r e e e q u i v a l e n t d e t e r m i n a n t s to get the 1 S s t a t e . T h e

" H . F . s e a " , the RHF s p i n - o r b i t a l s a r e {k} = {k e { l , 2, . . . M}}
Let u s c o n f i n e o u r s e l v e s to f i r s t - r o w a t o m s and i o n s , L i , B e , В , C ,
O, F , Ne, B e + , B e + 4 , B + , B + + so we h a v e l s n 2 s m 2 p k c o n f i g u r a t i o n s with
t h e r e s t r i c t i o n s t h a t n + m + k = N. We s h a l l take the s e t of M Roothaan
H . F . s p i n - o r b i t a l s a s the H. F . " s e a " .
With t h i s s e t we can c o v e r s e v e r a l h u n d r e d s t a t e s . T h e n u m b e r of
N - e l e c t r o n a r r a n g e m e n t s in M s p i n - o r b i t a l s i s
/м\ M! =
ш (33)
VN/ N! (М-N)! ~
IAEA - S M R - 1 2 / 5 2 67
B u t we h a v e only a l i m i t e d n u m b e r of d e t e r m i n a n t s ( k « m ) in Ф ш р
owing to s y m m e t r y .
We a l w a y s s t a r t f r o m a given H . F . s e a ; now we a r e d e a l i n g with
v a l e n c e c o n f i g u r a t i o n s giving o u r s p e c t r o s c o p i c s t a t e s .
We s e p a r a t e x CORR r i g o r o u s l y into t h r e e p a r t s
ф= + x I N T + XF + ХЦ (34)
RHF
and a l l f o u r t e r m s in x a r e m u t u a l l y o r t h o g o n a l
<XlI*m/=0 L ^ M L , M s { I N T , F , U, RHF}
=
XINT internal correlation
XF = s e m i - i n t e r n a l c o r r e l a t i o n including o r b i t a l p o l a r i z a t i o n s
хи = all external correlation
We h a v e a p a r t i a l l y f i l l e d " H . F . s e a "
~ ^RHF
H . F . " s e a " i n c l u d e s e v e r y t h i n g t h a t c o m e s f r o m the f i n i t e set of the

M s p i n - o r b i t a l s of the H . F . s e t . T h e p r o b a b i l i t y of f i n d i n g the s y s t e m
in Д к i s
~Pk = |C K f s 1 (35)
( e q u a l to 1 only if t h e r e is a s i n g l e det). T h e t o t a l w a v e f u n c t i o n can be

displayed as
X X X
^RHF CNT F u
T h e " i n t e r n a l c o r r e l a t i o n " i s a l l d e t e r m i n a n t s with H . F . s e a ( v i r t u a l

t r a n s i t i o n s to u n o c c u p i e d p a r t s of s e a ) .
T h e m u l t i - c o n f i g u r a t i o n SCF (MCSCF) i s a c o m b i n a t i o n i n c l u d i n g s o m e
p a r t s of <PRHF + XINT . but it g i v e s a n e g l i g i b l e i m p r o v e m e n t in e n e r g y f o r
a t o m s . M o r e g e n e r a l l y we h a v e
+
4>RHF XlNT
^GRHF
(37)
•Л + < % , т ! x i n t >
68 SINAN OG LU
b e c a u s e O R H F I^RHF ^ = r e n o r m a l i z e if w e w i s h to r e l a t e t o t h e 4>GRHF
( g e n e r a l r e s t r i c t e d H . F . d MCSCF) a s the s t a r t i n g point which is m o r e
u s e f u l in d i s s o c i a t i n g - m o l e c u l e p r o b l e m s .
T h e Xp, s e m i - i n t e r n a l p a r t , t a k e s a p a i r with one e" going out, t h e
o t h e r i n s i d e t h e s e a . B u t now t h e f u n c t i o n ( " o u t s i d e " ) , w h e r e the j - t h s p i n -
o r b i t a l e l e c t r o n g o e s t o , d e p e n d s on w h e r e t h e i - t h e l e c t r o n w e n t t o : so
i -> Л and j -> f i j | { ( X j )
a n d f i s o r t h o g o n a l to s e a o r b i t a l s
<fij { |k> =0, k e {1,2 M}
T h e s e m i - i n t e r n a l c o r r e l a t i o n e f f e c t w a s m i s s e d p r e v i o u s l y in a t o m i c
t h e o r y u n t i l it w a s d i s c o v e r e d b y the p r e s e n t t h e o r y in t h e a u t h o r ' s w o r k .
W h e n f i r s t c a l c u l a t e d b y t h e a u t h o r and B . Skutnik, it t u r n e d out t o b e a n
i m p o r t a n t e f f e c t c o m p a r a b l e in m a g n i t u d e t o t h e o t h e r two c o r r e l a t i o n
e f f e c t s we h a v e s e p a r a t e d .
F o r a l l - e x t e r n a l c o r r e l a t i o n s the p a i r t e r m s again a r e dominant just
a s in t h e c l o s e d s h e l l ( M E T ) t h e o r y .
<тдц|к> = 0 orbital orthogonal ke{l,2,...M}
A s W i g n e r noted, e x c i t e d - s t a t e c o r r e l a t i o n s looked v e r y c o m p l i c a t e d —
t h e r e s e e m e d to be no s y s t e m a t i c s . B u t now we k n o w t h i s i n d i v i d u a l i s t i c
b e h a v i o u r c o m e s f r o m x I N T a n d XF w h i c h we can c a l c u l a t e and a r e l e f t
w i t h only c l o s e d - s h e l l - t y p e х ц with t r a n s f e r a b l e p a i r s . A l l t h r e e t e r m s
a r e e q u a l l y i m p o r t a n t in e n e r g y .
In Xp a n o t h e r t e r m e x i s t s which we c a l l " o r b i t a l - p o l a r i z a t i o n " a n d
w h i c h w a s n e g l i g i b l e f o r c l o s e d s h e l l s , b u t h e r e it i s r e l a t i v e l y i m p o r t a n t .
It i s r e l a t e d t o f i j t b y s y m m e t r y s o it m u s t b e i n c l u d e d in Xf.
The exact e n e r g y is
E = ERHF + EINT + E F + ЕЦ (38)
but we m u s t r e s o r t to t h e s u b v a r i a t i o n a l p r i n c i p l e a g a i n to get t h e n o n -
c l o s e d s h e l l e n e r g y . We f i n d s t a t i o n a r y s o l u t i o n s (you do not n e c e s s a r i l y
h a v e an u p p e r b o u n d now) f o r e a c h c o r r e l a t i o n p a r t w i t h t h e v a r i a t i o n a l
energy
E E E r N C ( 3 9
E = ERHF + INT + F + u + )
w h e r e a g a i n R N C i s the r e m a i n d e r ( a s in t h e c l o s e d s h e l l c a s e ) b u t it i n c l u d e s
a l s o s o m e c o u p l i n g t e r m s b e t w e e n t h e e f f e c t s . F o r r o u g h l y the s a m e
r e a s o n s a s in c l o s e d s h e l l s , it should b e s m a l l , b u t we h a v e no d i r e c t
n u m e r i c a l e s t i m a t e , o n l y i n d i r e c t e v i d e n c e (cf. s e c t i o n 4).
IAEA - S M R - 1 2 / 5 2 69
W e c a l c u l a t e f i r s t t h e t h r e e t e r m s , Е и i s t h e s a m e a s in c l o s e d - s h e l l s .
How t o c a l c u l a t e E I N T and E F ? One c a n v a r y E F t o o b t a i n an i n t e g r o -
d i f f e r e n t i a l E u l e r e q u a t i o n f o r t h e fjj ^. S i l v e r s t o n e t r i e d t o s o l v e t h e s e
E u l e r equations n u m e r i c a l l y f o r s m a l l a t o m s but we shall p r o c e e d d i f f e r e n t l y .
We take the " c h a r g e - d e n s i t y wave function" which we introduce a s
= = < W + *INT + (40)
T h e \ > h a s n o s t r o n g e f f e c t on t h e c h a r g e d i s t r i b u t i o n s a n d r e l a t e d p r o p e r t i e s .
F o r e x a m p l e , f o r the t r a n s i t i o n probabilities it i s sufficient to u s e
F o r the e n e r g y we need Е ц a l s o . We have the H . F . - s e a Orbitals (including
t h o s e in t h e x I N T p a r t )
l s
a 2Pzß
M H.F. spin-orbitals
p l u s " s e m i - i n t e r n a l O r b i t a l s " f y к- T h e s e m i - i n t e r n a l O r b i t a l s could c o m e

f r o m the i n t e g r o - d i f f e r e n t i a l e q u a t i o n s m e n t i o n e d a b o v e , but we r e m e m b e r
t h a t <^RHF h a s t h e SU(2) 0 0(3) s y m m e t r i e s , but not t h e f ; . t , s o w e e x p a n d
them as
fi^fSi) = ^ fL(r) YLM(Q)ai (41)

L
T h i s e x p a n s i o n l o o k s only a s if it w e r e i n f i n i t e b u t it i s not b e c a u s e if
фрщр h a s a c e r t a i n s y m m e t r y ( f o r e x a m p l e , XS), xF h a s a l s o a S s y m m e t r y .
So in j ď (12 . . . Í. f i ( . . N) and t h e e x p a n s i o n of f.. { u s i n g v e c t o r c o u p l i n g ,
g i v e s only a f i n i t e n u m b e r of t e r m s in the e x p a n s i o n . O n l y L = 0, 1, 2, 3
f o r the K L s e a . Then we h a v e f s ( r ) , fp(r), fd(r) and f f ( r ) and that is all.
T h e r e would b e a s e t of s u c h r a d i a l f u n c t i o n s f o r e a c h i j however there
a r e not m a n y p o s s i b l e c o m b i n a t i o n s . So u s u a l l y only one s e t e x i s t s in t h e
K L - s h e l l s b e c a u s e of s y m m e t r y .
W e u s e a c o m b i n a t i o n of S l a t e r o r b i t a l e and t h e v a r i a t i o n a l m e t h o d f o r
e a c h f ( r ) , i . e . a n e x p a n s i o n in S T O ' s . C o r r e l a t i o n i s a s e c o n d - o r d e r
e f f e c t and h e n c e not v e r y s e n s i t i v e to the " s e a - o r b i t a l s " . F o r i n s t a n c e ,
t a k e a s i n g l e 3*í S. Т . O. b u t with a v a r i a t i o n a l e x p o n e n t (which w i l l c o m e
out v e r y d i f f e r e n t f r o m t h e r e a l 3 i exponent)
f(r) - 3*i
W e c a n now e v e n p a s s o v e r to t h e M - s h e l l u s i n g t h e l a r g e s t c o m p u t e r s .
P r o g r a m s d e v e l o p e d f i r s t b y O. Sinanoglu and I. Ö k s ü z , h a v e now b e e n
e x t e n d e d t o h e a v i e r a t o m s b e y o n d s o d i u m by O. Sinanoglu and D. B e c k .
S t a r t i n g f r o m t h e H . F . s e a a n d i n f o r m a t i o n of s t a t e , n u m b e r of e l e c t r o n s ,
e t c . , the f u l l y a u t o m a t i c p r o g r a m s c o m p u t e t h e "xF t e r m s b y v e c t o r c o u p l i n g .
F i r s t it g e t s a l l t h e i n t e r n a l a n d s e m i - i n t e r n a l d e t e r m i n a n t s . It u s e s t h e
Condon-Shortly m e t h o d s , spin p r o p e r t i e s , diagonalizes the large m a t r i x
and c o m p u t e s t h e c o e f f i c i e n t s , t h e n i t e r a t e s (only a b o u t 3 i t e r a t i o n s n e e d e d ) .
FLUORINE 111 152 2S 2P4 QUARTET p 07/13/72
COEFFICIENT
BET HF >A С ISA 1SB 2SA 2Р-А 2P0A 2P0B ?Р»А r.sooooooo
COEFpI СIENT CONTRIBUTIONS
«.U. E.V.
DFT г «* ISA 1SU 2S6 2P-A 2P0A гР»А ЗРПА ) .02041446 -7.63356174Е "04 -г. ,07707363Е- 02
DFT 3»A ISA J.SH 2P-A 2P-H 2I'0A ÍP->A ЗП+А ) V.01963041 "1'22«9204?E "03 -3 .33297906Е-•02
DFT 4 cA ISA ISB 2P.A 2P0A 2P.A гр«в 3D-» ) • .01963041 -1.22492042Е -03 -3,,332'79о6Е. 02
DFT Ç.A ISA jSH 2SA 2SB 2P0 A гР-А 3D-A ) « .0SB»Bie0 •8«13475435^ "03 -2.• 21344 714 Е-01
UFT 6 EA ISA IS!) 2SA 2P-U 2P 0 A ?Р*А 3P0A ) .010*4621 -1.56467937Е -04 • 4,, 257455 0 ОЕ-• 03
DET 7s A ISA 1SH 2SA 2P-H 2РПА гР*А 4F0A ) .01387797 -1.3015082бЕ "04 -3..54l37274E- 03
DET fl»A ISA ISB 2SA 2P0A PP.A гр-в 4ř-2A ) .00708017 -4.33U36067E -04 -1.Л8045758Е. 02
DET 9e A ISA 1S4 2SA 2SU A гр.А 35« ) 9 .03463341 -1.JB23543BE "03 -3. 7Í13530«E- 02
DFT 10aA ISA ISH 2SA 2S3 2P-A 2Р*А 3 DO А ) .00775990 -1.0M633Ç1E -02 -2,1951262в5Е- П1
DFT 11 3=A ISA ISH 2SA ?P-A 2P-B ÍP»A ?Р +А ) • .00508411 •7.2673S093E -05 •1.97742875Е. 03
DFT 1? A ISA IS» 2SA 2P-A Rl'-M гР»А 4F»A ) .0 06^3270 •3.470бВв70Е "04 •9.•«4366065Е- (13
DET 13 =A ISA 1SH 2SA 2P-A 2P+A гр»в Зр-А ) .00508411 •7.2673Ь093Е -05 •1.97742P75É- 03
DFT 14»A ISA iSH 2SA 2P-A 2P*A ЕР«В 4F-A ) • ,0»бЗЗ?70 •3.47068В70Е "04 -9,.44366065Е- 0 3
DET lb=A ISA IS4 ZSA 2Sb ? Г-А £Р 0 А ЗП»А ) » .05868180 -8,134754356 -03 -2.21344714Е-П1
DET 16=A ISA J.SH 2SA 2P-A p p - n ÎPOA 4F»2A ) • .0»7UBni7 -4.338360Й7Е -04 -1. IB045758E- 0 2
DFT 17 = A ISA ISH 2SA 2P-A 2K0A с P* H ЗРО А ) .U10 V4621 •1.56467937Е "04 -4 ,,25745500Е- 03
DET 1P = A ISA ISH 2SA ?.P-A ?P0A ЕР*В 4F 0 А ) .003«7797 -1. 301508261: -04 -3,,54137274Е..03
DFT 19=A ISA isa 2P-A 2P0B гр-А ?ЗА ) .00099959 •1.4J. 2В7427Е -06 •3' •844396986- 05
DFT 20=A ISA 1SÍI 2P-A 2Р0Л
Р 2Р* А 3|)П4
2P0B ) * ,оггбб725 -1.63322722Е - 0 3 •4 ,,44397200Е- 02
DET 2 l = A ISA ISH 2SA 2 0А 2l'0« ?Р* А ЗР-А ) .015?4?96 -4. Ц693765Е "04 -1. 1?0?0885Е- 02 8.
P
DFT 22*A ISA 15П 2SA 2 0A ZPOti ГР*А 4F-A ) . 00633270 -3.47068870E'-04 •9. 4 4 366Р65Е-03 E
DET 23aA ISA I S il 2SA гг'» ГР0Н ЕР»А ЗРОА ) . 00 0*8736 -1.02395618Е "06 -2. 78616019Е- 05
DET 24»A ISA ISB 2SA 2P-A 2''OH ŘP+Л 4F0A ) • .00775594 -5.20603304Е "04 -1.•41654910Е- о г
DFT 2Г = А ISA 1SIJ 2S« 2P-A 2P0A 2Р-А 3|>0В ) » .0+2^9424 .2.91798618Е -03 .7. 93977037Е- 0 2
DET 26eA ISA IS'1 2SÍ 2Р-Л 21'OA ;Р«А 4Г0В ) W ., 00000000 1.2270397.76-31 3. 33874577Е- 30
DET 27«A ISA isa 2SA 2P'A 2P0A ?РОВ 3|>»А ) • .01554296 •4.Ц693765Е'"04 -1. 12020Вв5Е- 0 2
DET 2E sA ISA 1SÍ) 2SA 2P-A 2P0A ZP0IÎ 4Г»А ) » .006^3270 •3.47068870Е'•04 •9. 44366065Е- 03
DET 29«A ISA ISH 2se 2P-A 2''0 A ГР*А 4Г0А ) .00000000 0. 0.
EHF(A.U,î a -9.69143342F+01
ETOTALU-U,) » -9.6951917(IE*01
DIFFERENCE!»,U,) > .4.05B35725E-0?
EXPONENTS 3S « г . о з г п о о о CONTRIBUTIONS -1.3«374725E-03
3P • 1•6020000 -*.9È40JI6'3E.03
3D в 2.6750 000 .3.119Н«13УЕ.02
IF з 4.2260000 ,5.03бВ52*1Е.03
REMORMALIZATION FACTOR > .99146072

FIG. 1. Direct computer output for the charge wave function 4<c of the n o n - c l o s e d - s h e l l - m a n y - e l e c t r o n
theory [ 1] of Sinanoglu for the Is2 2s2p4 4 P of fluorine III. T h e orbitals labelled as 3s, 3p, 3d, and 4f refer
to the s e m i - i n t e r n a l orbitals f s , f , f d , and f f described in the text.
IAEA -SMR-12/52 71
F i g u r e 1 s h o w s an e x a m p l e of a d i r e c t c o m p u t e r output ¥ c , the " c h a r g e

wave f u n c t i o n " (i. e. " c h a r g e - d i s t r i b u t i o n w. f. ") of an a t o m i c s t a t e . O u r
a u t o m a t i c p r o g r a m s h a v e p r o d u c e d s e v e r a l h u n d r e d such wave f u n c t i o n s
f o r m o s t s t a t e s of i n t e r e s t in a t o m i c t h e o r y . We t h u s h a v e now an a t l a s
of a t o m i c s t r u c t u r e s with f u l l c o r r e l a t i o n , which y i e l d the a c c u r a t e a t o m i c
properties. T h e new s i t u a t i o n m a y b e c o n t r a s t e d with the p r e v i o u s
l i t e r a t u r e w h e r e h a r d l y one such wave f u n c t i o n e x i s t e d .
C o m p u t e r t i m e i s r o u g h l y 30 s e c o n d s p e r s t a t e on the CDC 6600
c o m p u t e r f o r s e c o n d - r o w a t o m s . We h a v e now s t i l l two p r o b l e m s : how
and how w e l l c a n we c a l c u l a t e t r a n s i t i o n p r o b a b i l i t i e s , and how c a n we
obtain Ец which i s s t i l l a l a r g e p o r t i o n of t h e c o r r e l a t i o n e n e r g y .
4. T H E A L L - E X T E R N A L C O R R E L A T I O N Е ц AND E N E R G Y L E V E L S
In the l a s t s e c t i o n we s u m m a r i z e d the t h e o r y f o r n o n - c l o s e d s h e l l
s t a t e s in the v e r s i o n a p p l i c a b l e to a t o m s and s t a b l e m o l e c u l e s . We h a v e
s e e n two s t a r t i n g p o i n t s , one of t h e m b e i n g the r e s t r i c t e d H a r t r e e - F o c k
m e t h o d (RHF):
к <m
ФRHF = У Ск Д к (42)
Ksi
In t h i s c a s e the c o e f f i c i e n t s a r e a l l d e t e r m i n e d by 0(3) X SU(2) r
s y m m e t r y a l o n e . In the o t h e r c a s e of the g e n e r a l r e s t r i c t e d H a r t r e e -
F o c k (GRHF) m e t h o d we h a v e a g a i n a l i n e a r c o m b i n a t i o n
m
c л
Фскнг = X k к C43)
к
but h e r e the c o e f f i c i e n t s a r e not d e t e r m i n e d by 0(3) s y m m e t r y a l o n e , they
a r e d e t e r m i n e d in p r i n c i p l e by s o m e h i g h e r g r o u p s [12, 13] o r j u s t by
c a l c u l a t i o n . At t h e m o m e n t t h e s e c o e f f i c i e n t s a r e obtained only via m a t r i x
d i a g o n a l i z a t i o n by c o m p u t e r s .
In a t o m s t h i s s t a r t i n g point i s not r e a l l y n e c e s s a r y , b e c a u s e t h i s i s
quite a c c u r a t e l y given by
I A $RHF + * INT
GRHF
" s/l
V I + 4< У Ix—7
INT ' INT
<44>
but with m o l e c u l e s which a r e d i s s o c i a t i n g we cannot do t h i s .

F o r a t o m s , a s we s a i d , we s t a r t with ф к н р . T h e n the exact wave
function is
¥ = + X + X + w i t h
" W INT F V < Ф > = 1 + <x|x> (45)
w h e r e x F i s s e m i - i n t e r n a l and o r b i t a l p o l a r i z a t i o n and x is all external.

72 SINANOGLU
The energy is also
E = E r h f + E[NT+f + Ец (46)
We can c a l c u l a t e the f i r s t two t e r m s u s i n g the H . F . and our " s e m i -

i n t e r n a l o r b i t a l s " and then get Е ц l a t e r .
We can c a l c u l a t e E I N T and E F s e p a r a t e l y o r t o g e t h e r . T h e d i f f e r e n c e
i s not e s s e n t i a l and we let the c o m p u t e r c a l c u l a t e it in one r u n .
It r e m a i n s to obtain the Е ц p a r t , w h e r e we have a c l o s e d - s h e l l - l i k e
s i t u a t i o n , m a i n l y p a i r c o r r e l a t i o n s c a u s e d by s h o r t e r - r a n g e f l u c t u a t i o n
p o t e n t i a l s . ( T h i s i s not t r u e f o r Е ш т o r E p w h e r e the h i g h e r e l e c t r o n
t e r m s are important. )
F o r c l o s e d - s h e l l s we had
Л a n d E e ( 4 7 )
^RHF = 1 U = X ii
i >j
F o r t h e c a s e of n o n - c l o s e d s h e l l s
r
RHF
С
к л к ; Eu = X Pi
i +
)_. Pij;kJ2
€
ij;ki
(48)
ijke
We h a v e t h e H a r t r e e - F o c k s e t c o n s i s t i n g of
{k} = { ( I s 2 s 2 p ) X ( a , ß ) } dim M s N (49)
with s y m m e t r y 0 ( 3 ) X SU(2) o , and all p^ c o e f f i c i e n t s a r e d e t e r m i n e d by

symmetry.
T h e p;j a r e
T h e sum i s only o v e r such К which contain i, j s p i n - o r b i t a l s .

T h i s i s the p r o b a b i l i t y f o r the occupation of the i, j s p i n - o r b i t a l s in
'PRHF •
Py. k j i s a new t e r m in the n o n - c l o s e d s h e l l b e c a u s e t h e r e a r e now
" c r o s s pairs" or off-diagonal pairs.
In the c l o s e d - s h e l l c a s e , when we m i n i m i z e the 2e~ - p a r t u p p e r bound
е.. s (51)
и ч
w h e r e e,, i s given by
e
ij = < ^ 1 2 ( 4 ) ! ~ l û u >
ij
IAEA - S M R - 1 2 / 5 2 73
и - i s t h e f u n c t i o n w h i c h m a k e s e^ a m i n i m u m . S i m i l a r l y , we h a v e
e
ij;ki = < - * У ч > I ZT7 I û k f i > (52>
we r e m e m b e r
j*12(ij) = {i(Xi) j(3j)}

JT
N o t e t h a t w e c a n t a k e g 1 2 i n s t e a d of ш ц = g 1 2 - §i(2) - S 2 ( l ) + J i 2 , b e c a u s e
J 1 2 f a l l s out u p o n i n t e g r a t i o n and a l s o S 1 (2) b e c a u s e of o r b i t a l o r t h o g o n a l i t y .
T h e Pij. k £ a r e e s s e n t i a l b e c a u s e of s y m m e t r y . If you d r o p t h e m , t h e
e q u a t i o n b e c o m e s i n c o n s i s t e n t , you l o s e t h e i n v a r i a n c e p r o p e r t i e s w h e n
you c h a n g e c o - o r d i n a t e s
C
Pij-Mt = I KCL; (i.j)6AK. (k,i)EAL (53)
К ^L
F o r c l o s e d - s h e l l s we h a v e o n l y one d e t e r m i n a n t A j , P j = 1 p k ? ! 2 = 0;
s o pjj g i v e s a f a c t o r of 1 a n d ру. к 4 i s z e r o , i s a l m o s t the s a m e , e. g.
f o r B e , B e + , B e 2 + , i. e. it i s t r a n s f e r a b l e . B u t the P ; j . k i p a r t c a n m a k e
a difference.
T o s e e h o w we can e v a l u a t e t h e c r o s s p a i r s , l e t u s c o n s i d e r c a r b o n
ls22s2 (2p2+2p2+2p2).
S u p p o s e you t a k e now a l l the p a i r s
T h e i n d i v i d u a l o r b i t a l s b e l o n g to 0(3) X SU(2) but the function

^ 1 2 ( 2 р ^ 2p® ) t r a n s f o r m s a s [0(3) X SU(2) 0 ] X [0(3)"x SU(2) Ö ], b u t , of c o u r s e ,
t h e r e p r e s e n t a t i o n i s r e d u c i b l e . B u t we c a n t r a n s f o r m t o the i r r e d u c i b l e
r e p r e s e n t a t i o n of 0(3) X S U ( 2 ) 0 . So we c a n s a y t h a t
= reducible pairs
2
If we h a v e 2p in s e v e r a l r e d u c i b l e p a i r s , w e c a n m a k e a u n i t a r y
t r a n s f o r m a t i o n to obtain the following i r r e d u c i b l e p a i r s :
(2p2) -> 1
2
(2p ) -> 5 15 w a v e f u n c t i o n s (54)
(2p 2 ) 3 P -> 9
T h e a d v a n t a g e i s , of c o u r s e , i n ' t h e e x p r e s s i o n of t h e e n e r g y
E
u => ei
74 SINANOGLU
w h e r e I r u n s o v e r a l l i r r e d u c i b l e p a i r s , e. g.
e
i = e 2pî 1 s =<ф(2р 2 , 1 s)| I Û2p2 i s > (55)
12
b e c a u s e the û ' s t r a n s f o r m the s a m e way a s the i, j.

The c r o s s t e r m s a r e
e
i.I lr-|GI> =0 ' (56)
1.2
b e c a u s e they b e l o n g to d i f f e r e n t i r r e d u c i b l e r e p r e s e n t a t i o n s and r-^ i s

s p h e r i c a l l y s y m m e t r i c , s o it g i v e s z e r o .
Only one " c r o s s e d p a i r " r e m a i n s in the K L - s h e l l s , n a m e l y
2
^ s ) « ^(гр2)
T h u s one cannot obtain a l l the Ру к{ by s y m m e t r y u n l e s s a l a r g e r g r o u p is

found, but t h i s s t i l l i s an open p r o b l e m . So
^ =I e
i +
I ßa
'
£l1
' (57)
i i?i>
F o r m o s t s t a t e s the second t e r m s do not even a p p e a r , even when they

e x i s t you e i t h e r e s t i m a t e t h e m o r c o n s i d e r t h e m s m a l l . So the p r o b l e m
i s to c a l c u l a t e
I 0 . ei
l
The cross pair
<cp(2s 2 1 S)| —
r
|û(2p 2 1 S)>
12
w a s e s t i m a t e d by s e v e r a l m e t h o d s [14] f o r Ne to t e s t h y b r i d i z a t i o n of the
type u s e d in CH 4 . C h e m i s t s suppose the t e t r a h e d r a l i n t e r - o r b i t a l c o r r e l a t i o n s
t o be s m a l l , but t h i s h a s t u r n e d out to b e w r o n g e v e r y t i m e a c a l c u l a t i o n
h a s b e e n m a d e . So a l l the p a i r c o r r e l a t i o n s a r e n e e d e d a s p r e d i c t e d in o u r
t h e o r y . T h e c h e m i s t s ' " s e p a r a t e d - p a i r " a s s u m p t i o n b a s e d on e l e c t r o n - p a i r
b o n d s only, i s i n c o r r e c t .
F o r a l l s t a t e s in L s h e l l of the type l s 2 2 s n 2 p m , i. e. B , C, N, O, etc.
and t h e i r i o n s , we h a v e E RHF + E I N T + E F and E. e x p , i s a l s o a v a i l a b l e ( f r o m
M o o r e ' s t a b l e s m a k i n g r e l a t i v i s t i c c o r r e c t i o n s ) . So one can get Е и
(experimental)
E u ( e x p ) - > У ß { e, efP(Z) (58)

l
IAEA - S M R - 1 2 / 5 2 75
T h e /3] a r e d e t e r m i n e d by g r o u p t h e o r y , so one d e t e r m i n e s e®xP and u s e s

this to r e c a l c u l a t e t h e s a m e s t a t e s and a l s o o t h e r s that w e r e not u s e d
(cf. the s e r i e s in P h y s . R e v . s t a r t i n g in 1969) (cf. Sinanoglu and O k s ü z ,
P h y s . Rev. L e t t . 21_, (1968) 597);
magnitude E ö ~ 3 - 5 eV
deviation ě 0.02 eV
T h e r e s u l t s f o r i r r e d u c i b l e p a i r c o r r e l a t i o n s in a t o m s a r e shown in
T a b l e II. It can b e s e e n that they a r e i n s e n s i t i v e to c h a n g e s in Z.
A p r e d i c t i o n of o u r t h e o r y i s that
w h e r e we n e g l e c t R ' , i. e. we c o n s i d e r decoupled p a i r c o r r e l a t i o n s (only

f o r Е и ) . We s u p p o s e a d d i t i v i t y and t r a n s f e r a b i l i t y of e a c h e. T h e f a c t
that f r o m the t a b l e in " A t o m i c P h y s i c s " [ l ] we can get good p r e d i c t i o n s
and that Е ц i s obtained with a d e v i a t i o n TO.02 eV m a y b e c o n s i d e r e d a s an
i n d i r e c t proof of t h i s .
We w i l l r e v e r s e the p r o c e d u r e now to give a m e t h o d f o r t h e c a l c u l a t i o n s
of v a r i o u s a t o m i c p r o p e r t i e s .
We f i r s t d i s t i n g u i s h b e t w e e n two b r o a d c l a s s e s of p r o p e r t i e s . (This
i s not a r i g o r o u s d i v i s i o n , but a quite p r a c t i c a l one.)
allowed t r a n s i t i o n s
forbidden transitions
spin d e n s i t y
- = " c h a r g e - l i k e " p r o p e r t i e s (gj) (59a)
absolute charge density
hyperfine constants
multipole moments
and
energetics
EA
IP = " e n e r g y - l i k e " p r o p e r t i e s (g 12 ) (59b)
i n n e r IP
excitation energy
E n e r g y - l i k e p r o p e r t i e s depend on c o r r e l a t i o n m u c h m o r e than c h a r g e -
like p r o p e r t i e s which a r e given b y the o v e r a l l c h a r g e d i s t r i b u t i o n .
We s t a r t with the p r e d i c t i o n that
Ш = Ш (60)
CD "
t h i s i s a l l one n e e d s f o r c h a r g e - l i k e p r o p e r t i e s ; f o r e n e r g e t i c s , h o w e v e r ,
one should u s e the c o m p l e t e f u n c t i o n .
We a l w a y s t e s t the p r e d i c t i o n s by m a k i n g a c a l c u l a t i o n f o r a new
s t a t e (or s t a t e s not u s e d in t h e t a b l e in " A t o m i c P h y s i c s " (1969).
T A B L E II. I R R E D U C I B L E A L L - E X T E R N A L P A I R C O R R E L A T I O N E N E R G I E S O B T A I N E D
F R O M L E A S T - S Q U A R E S ANALYSIS O F G R O U N D - C O N F I G U R A T I O N A L L - E X T E R N A L
ENERGIES ONLY
e (2s-*-2p) 21
e(ls2) 6(1S2-2S) e(ls2-2p) e(2s2) <=(2p2;3p) «(2 P VD) e(2p ; S)
c(2s2p;3p) e(2s2p;Xp)
В 1.221 0.104 0.102 0.060 0.421 - - -
0.131 0.449
с 1.240 0.090 0.102 0.102 0.407 0.282 0.591 1.107

0.121 1 Ů.H0
N 1.256 0.071 0.102 0.147 0.420 0.244 0.589 1.165

0.118 1 0.485
0 1.261 0.082 0.102 0.190 0.431 0.219 0.556 1.111
0.104 1 0.551
F 1.266 0.079 С. 102 0.230 0.446 0.201 0.541 1.106

0.100 1 0.592
Ne 1.268 0.085 0.102 0.275 0.448 0.192 0.563 1.133
0.100 1 0.596
Na 1.274 0.083 0.102 0.318 0.471 0.168 0.594 1.149
0.100 1 0.642
e ( l s ? - » 2 s ) = [ 3 6(ls2s; 3 S) + e ( l s 2 s ; ' S ) 3 / 2 a n d t í l s ^ ž p ) = [ 3 e ( l s 2 p ; 3 P) + e ( l s 2 p ; ' p ) ] / 2 . For Boron t h r o u g h o x y g e n s e p a r a t i o n

of e(2s 2 -» 2p) i n t o e(2s2p; 3 P) a n d e(2s2p; !p) is o b t a i n e d b y a s s u m i n g the s a m e £(2s2p; 3 P ) / e ( 2 s 2 p ; >P) r a t i o as o b t a i n e d f r o m
analysis of all ground + e x c i t e d c o n f i g u r a t i o n s . In F , N , a n d N a e(2s2p; зр) a r e a s s u m e d t o r e m a i n - 0 . 1 e V . [ e ( 2 s 2 ) a l l - e x t ]
values a r e f r o m V. M c K o y a n d O . S i n a n o g l u , J. C h e m . Phys. 4 1 , (1964) 2 6 8 9 ; e ( l s 2 - » 2p) is f i x e d at the o x y g e n v a l u e by
H. P. K e l l y , Phys. Rev. 144, ( 1966) 39. s i n c e t h e s e s m a l l q u a n t i t i e s would b e t o o s e n s i t i v e in a l e a s t - s q u a r e s f i t .
IAEA - S M R - 1 2 / 5 2 77
T A B L E III. I N T E R N A L ( E I N T ) . S E M I - I N T E R N A L ( P L U S T H E S M A L L O R B I T A L
P O L A R I Z A T I O N S = E f ) AND T H E " E X P E R I M E N T A L " A L L - E X T E R N A L
C O R R E L A T I O N E N E R G I E S IN SOME S T A T E S AND IONS O F N I T R O G E N AND
OXYGEN
2 2 2 2 2 3 2 2
Is 2s 2p Is 2s 2p Is 2s2p
CONFIGURATION
STATE 3 4 2 2 4
P *D 2
S 2
P
P b> S D P
E
int -0.58 -0.56 -2.15 0.00 0.00 -0.95 0.00 0.00 0.00 0.00
Z = 7 Ef -1.14 -1.15 -0.07 -1.28 -1.31 -0.59 -0.14 -1.13 -0.18 -1.60
Eu("exp") -2.83 -3.18 -3.74 -3.84 -4.35 -4.76 -1.97 -2.40 -3.22 -2.54
E -0.68 -0.67 -2.57 0.00 0.00 -1.17 0.00 0.00 0.00 0.00
int
Z = 8 Ef -1.20 -1.23 -0.05 -1.40 -1.45 -0.64 -0.15 -1.14 -0.14 -1.64
Eu("exp") -2.88 -3.27 -3.80 -3.85 -4.35 -4.76 -2.13 -2.52 -3.28 -2.68
E x a m p l e s of o r d e r s of m a g n i t u d e s f o r d i f f e r e n t t e r m s , e. g. f o r
Z = 7; N = 7 ; ls22s22p3<^ : 2
D
4 4
S
a r e given in T a b l e III.
In g e n e r a l the t h r e e t e r m s a r e b a s i c a l l y c o m p a r a b l e .
L e t u s now a n a l y s e s e v e r a l c a l c u l a t i o n s of t e r m - s p l i t t i n g r a t i o s .
F i r s t u s i n g F a n d G i n t e g r a l s (without c o r r e l a t i o n ) a s in C o n d o n - S h o r t l e y ' s
or Slater's books for
'S
2 2 J
Z =6 lsř 2s 2p D
o n e f i n d s the r a t i o R = S D / D P = 1.5. M a k i n g a s e p a r a t e H . F . c a l c u l a t i o n
f o r e a c h t e r m , t h e r a t i o c h a n g e s b y 1 o r 2%, u s i n g the u s u a l C . I. o r
M C S C F one a l s o g e t s 1 - 2 % . C o m p a r i n g w i t h e x p e r i m e n t s , w e n o t e t h a t
t h e C o n d o n - S h o r t l e y - H a r t r e e - F o c k - M C S C F m e t h o d s w o r k f o r low c o n f i g u -
r a t i o n s but f a i l f o r h i g h e r c o n f i g u r a t i o n s . C o n s i d e r , e. g.
78 SINANOGLU
Z =6 I s 2 2s2p R =
F and G m e t h o d g i v e s 1.5
B a c h e r - G o u d s m i t method gives 4.34
Layser Z-dependent theory 1.45 (61)
Experim ental 2.3

Our theory 2.75
E r r o r s in e l e c t r o n a f f i n i t y a r e a l s o of the o r d e r of 10-15% while H . F .

y i e l d s a w r o n g sign.
U s i n g the l a r g e new p r o g r a m by O. Sinanoglu and D. B e c k we can go
to 3 r d - r o w a t o m s (i. e. Mg, Al, Si, . . . ) and a l s o r e c a l c u l a t e 2 n d - r o w
a t o m s m o r e a c c u r a t e l y and we can study h i g h e r e x c i t a t i o n s .
5. TRANSITION P R O B A B I L I T I E S
So f a r we c o v e r e d the t h e o r y of g r o u n d s t a t e s and then we s u m m a r i z e d

the t h e o r y of e x c i t e d s t a t e s . We c a l c u l a t e d the d i f f e r e n t c o r r e l a t i o n
c o n t r i b u t i o n s to open s h e l l s y s t e m s . We c o n s t r u c t e d the " c h a r g e -
d i s t r i b u t i o n wave f u n c t i o n "
+ X
^c - ^CD" ^RHF INT+ F
F u r t h e r we showed that t h e a l l - e x t e r n a l c o r r e l a t i o n in e n e r g y could b e

c a l c u l a t e d in the s a m e way a s f o r the c a s e of closed s h e l l s y s t e m s .
We s h a l l d i s c u s s now s e v e r a l t o p i c s :
(1) T h e t r a n s i t i o n p r o b a b i l i t i e s . We c o n s i d e r the new t h e o r y and new
e x p e r i m e n t s . We s h a l l d i s c u s s two k i n d s of t r a n s i t i o n p r o b a b i l i t i e s f o r
which the e x p e r i m e n t a l and t h e o r e t i c a l s i t u a t i o n is quite d i f f e r e n t :
(a) Allowed t r a n s i t i o n p r o b a b i l i t i e s
(b) F o r b i d d e n t r a n s i t i o n p r o b a b i l i t i e s
T h e s e t o p i c s a r e i n t e r e s t i n g f o r s e v e r a l r e a s o n s . T h e y have a p p l i c a t i o n s
in p l a s m a p h y s i c s , in a t m o s p h e r i c p h y s i c s and in a s t r o p h y s i c s . T h e y a l s o
give c o n f i d e n c e upon s u c c e s s f u l t e s t s of the t h e o r y of a t o m s , in s i m i l a r
molecular calculations.
Then we s h a l l c o n s i d e r
(2) S t a b l e - m o l e c u l e s binding e n e r g i e s .
So l e t u s s t a r t with the t r a n s i t i o n p r o b a b i l i t i e s .
We s h a l l not c o n s i d e r now c o l l i s i o n a l t r a n s i t i o n s t h a t m o d i f y t h e
l i f e t i m e s т . We u s e the s p o n t a n e o u s e m i s s i o n f o r m u l a :
(62)
Tm =
2 A,
n
.where e = ДЕ i s the e n e r g y d i f f e r e n c e , ûi i s the d e g e n e r a c y of the i n i t i a l

s t a t e and c ' i s v e l o c i t y of light (in a . u . 137), while S i s t h e line s t r e n g t h .
IAEA - S M R - 1 2 / 5 2 79
An a l t e r n a t i v e i s to u s e t h e o s c i l l a t o r s t r e n g t h
f=f ^ S
d Uj
S(yLS ^ y'L'S') (63)
F o r t h e l e v e l s of the l i g h t e r a t o m s one u s e s L S - c o u p l i n g and t h e j - j

s e p a r a t i o n i s not too l a r g e , s o one i s i n t e r e s t e d in m u l t i p l e t o s c i l l a t o r
strengths.
T h e u s u a l c a l c u l a t i o n s a r e b a s e d on the o n e - e l e c t r o n m o d e l w h i c h t u r n s
out i n a d e q u a t e , b e it R a c a h ' s m e t h o d or C o n d o n - S h o r t l e y 1 s. One h a s to
c a l c u l a t e t h e w h o l e N - e l e c t r o n m a t r i x e l e m e n t e v e n in t h e c e n t r a l f i e l d ,
i. e. t h e R H F a p p r o x i m a t i o n :
S(YLS Y'L'S') = ^ |< Y L S M l M J R I T ' L ' S ' M ; ivy > | 2 (64)
M l ,M s ,M' l , Mg
W e s t a r t with d i p o l e t r a n s i t i o n s E l . We c a n u s e e a c h of t h r e e o p e r a t o r s
to get t h e s e allowed t r a n s i t i o n s :
(i) 1 d i p o l e length г Й ï? ; f r = b e Sr
i=l
Л
(ii) velocity operator v =y Vj; fy = ь ^ s v (65)
i —1
(iii) acceleration f a = b -4- S,

» e
with
S r = |<i|?|f > | ? S v = | | 2 , Sa = | |*
and
v = -V -+ У
1=1
but one d o e s not n e e d t o c a l c u l a t e m a t r i x e l e m e n t s of ( 2 - e " ) - o p e r a t o r s

b e c a u s e t h e y c a n c e l out, owing to t h e f a c t t h a t t h e f o r c e a c t i n g on i - t h e"
1
T o e l i m i n a t e t h e d e p e n d e n c e on e , w e c a n a l s o c a l c u l a t e f = Vf r
80 SINAN OG LU
b e c a u s e of t h e j - t h one i s c a n c e l l e d by the f o r c e of i - t h e" a c t i n g on

j - t h e~. In f a c t we have
Vi У Z_
i V =
/ , r? r2
i=l i=l
s o the p o r t i o n n e a r the o r i g i n i s dominant in t h i s 3rd c a s e .

F o r the H - a t o m all t h r e e o p e r a t o r s give the s a m e r e s u l t . F o r the He
a t o m they a r e r e a s o n a b l y c l o s e .
T h e NBS t a b l e s r e p o r t m o s t l y H a r t r e e - F o c k c a l c u l a t i o n s with r e s u l t s
(f r and f v ) which a r e often w r o n g by about a f a c t o r of 2 c o m p a r e d to the
t r u e v a l u e s . T h e f a with with H . F . u s u a l l y d i f f e r s by a f a c t o r of 500. In
t h e NBS (3 v o l u m e s ) T a b l e s (1969) the r e s u l t s a r e often an a v e r a g e of
v a r i o u s e x p e r i m e n t a l v a l u e s and H . F . , o r m a y b e C . I . (a couple of c o n -
f i g u r a t i o n s a t m o s t by and l a r g e ) . But l a t e l y the new e x p e r i m e n t a l
t e c h n i q u e s and M E T c a l c u l a t i o n s a r e changing t h i s s i t u a t i o n .
Now we h a v e f o r i n i t i a l and f i n a l s t a t e s (a = i o r f)
+
CD " 'PRHF MNT +F
b u t we h a v e a l a r g e n u m b e r of d e t e r m i n a n t s in b r a and k e t f o r the t r a n s i t i o n
p r o b a b i l i t y m a t r i x e l e m e n t without o r t h o g o n a l i t y p r o p e r t i e s to help u s .
F o r i n s t a n c e we could h a v e an i n i t i a l s t a t e l s 2 2 s m 2 p n a s H . F . " s e a " and
the f s f p f d f f a s the a d d i t i o n a l s e m i - i n t e r n a l o r b i t a l e , going to l s 2 ' 2 s m ' 2p n '
with new o r b i t a l s that a r e n o n - o r t h o g o n a l to the e a r l i e r o n e s . H o w e v e r ,
a new l a r g e p r o g r a m h a s b e e n developed b y P . W e s t h a u s and O. Sinanoglu [2],
which i n v o l v e s i n i t i a l t r a n s f o r m a t i o n s of the n o n - o r t h o g o n a l o r b i t a l s and
d e a l s with t h i s p r o b l e m e f f e c t i v e l y .
P r e v i o u s l y only c a l c u l a t i o n s c o m p a r a b l e in m a g n i t u d e w e r e c a r r i e d
out b y W e i s s [15], f o r c a r b o n , u s i n g about 20 c o n f i g u r a t i o n s in С. I. , but
with the u s u a l d e f e c t s of the С. I. m e t h o d , so it w a s not s u f f i c i e n t l y
a c c u r a t e o r g e n e r a l . (The u s u a l С. I. k e e p s adding c o n f i g u r a t i o n s , but it
i s not c l e a r which to c h o o s e ; it i s slowly c o n v e r g e n t and m a y take into
a c c o u n t u n i m p o r t a n t o n e s and o m i t s i g n i f i c a n t o n e s , like the x s e m i - i n t e r n a l .
MET eliminates these defects.)
In the С - I I t r a n s i t i o n which we show h e r e a s an e x a m p l e ,
С II 2p 2 P ° -> 2p 2 2 D
j. RHF f RHF -NBS „new (66)
! 1
*r V exp
0.263 0.262 0.27 0.114
Without the new e x p e r i m e n t a l r e s u l t s one would r e a c h the c o n c l u s i o n that

one had v e r y good R H F r e s u l t s as f r , f v and " e v e n " f N B S c o i n c i d e . But
f"®p showed t h e v a l u e s to b e i n c o r r e c t . T h e a r g u m e n t t h a t RHF g i v e s the
s a m e r e s u l t s f o r d i f f e r e n t o p e r a t o r s , i s a l s o not t r u e g e n e r a l l y as we s e e
in a n o t h e r e x a m p l e ,
IAEA - S M R - 1 2 / 5 2 81
N III 2p 2 P° -> 2p 2 2 S
fRHF fRHF fNBS fej[p (67)
0.056 0.035 0.11 ?
Now let u s c o n s i d e r the new t h e o r e t i c a l (MET) c a l c u l a t i o n s of

Sinanoglu and W e s t h a u s :
f new jRHF fNBS jMET

о л 9 9
С II 2р Р -» 2р D 0 114 0 263 _ 0 1 2 5
N II 2р 2 3 Р -» 2р 3 3 D° { 0109 °-236 0 Л 7 0 Л 0
°
(68)
L e t u s now look at the e x p e r i m e n t s :

T h e t r a d i t i o n a l m e t h o d s w e r e of the e m i s s i o n o r a b s o r p t i o n t y p e s .
In o r d e r to d e t e r m i n e i n t e n s i t i e s f r o m e m i s s i o n one n e e d s the n u m b e r
of a t o m s v e r y a c c u r a t e l y ; a l s o f o r a b s o r p t i o n , and t h i s m a k e s the o l d e r
m e t h o d s u n r e l i a b l e , no b e t t e r than b y a f a c t o r of two. H o w e v e r , s i n c e
about 1965 new m e t h o d s h a v e c o m e about:
(1) B e a m - f o i l s p e c t r o s c o p y (BFS)
(2) P h a s e s h i f t m e t h o d
B a s h k i n (1965) developed B F S L16] . You a c c e l e r a t e ions (even with a
t a n d e m l i n e a r a c c e l e r a t o r , f o r example) and then n e u t r a l i z e t h e m o r s e l e c t
them, etc.
->x
atom beam
1 - 5 MeV
foil
In p a s s i n g t h r o u g h the thin f o i l , the a t o m s a r e e x c i t e d . How do they

r e t u r n to the ground s t a t e ? B y r a d i a t i n g a p e n c i l of light of d e c r e a s i n g
d e n s i t y along the b e a m a x i s .
T h e o b s e r v e d line i n t e n s i t y i s a function of d i s t a n c e and the l i f e t i m e т
i s obtained f r o m the r e l a t i o n
I(x) = I(XQ) E - x / " (69)
w h e r e I(x) i s the i n t e n s i t y of light along t h e b e a m at x and v is the b e a m

velocity.
82 SINANOGLU
If t h e p a r t i c u l a r p r o c e s s i s w e l l - k n o w n , e. g. t h a t t h e l i g h t i s known
t o b e due t o a s i n g l e t r a n s i t i o n i -> f, one a l s o h a s :
t =-£- (70)
if
and one o b t a i n s A w i t h a n a c c u r a c y of 3-10%. B u t one can h a v e a c a s c a d e

and h a v e a s u p e r p o s i t i o n of e v e n t s . So it i s c r u c i a l to h a v e a good i n t e r -
p r e t a t i o n . And h e r e the t h e o r y c o m e s in; in new t h e o r y we c a n r e a c h
a c c u r a c i e s of 3 - 1 0 % , s o w e c a n d i s t i n g u i s h b e t w e e n e x p e r i m e n t a l r e s u l t s
b a s e d on d i f f e r e n t i n t e r p r e t a t i o n s .
F o r e n e r g i e s a b o v e 5.5 M e V , one n e e d s a t a n d e m V a n - d e - G r a a f f
a c c e l e r a t o r o r a h e a v y - i o n l i n e a r a c c e l e r a t o r . O n e c a n get unknown l e v e l s
in h e a v y a t o m s , o r i o n s n e v e r o b s e r v e d in l a b o r a t o r y b e f o r e . In a s t r o -
p h y s i c s , 20% of t h e o b s e r v e d s o l a r u . v . l i n e s h a v e not b e e n i d e n t i f i e d a s
l i t t l e i s known a b o u t h e a v y i o n s . So t h i s i s a v e r y f r u i t f u l f i e l d .
B e y o n d the A r a t o m r e l a t i v i s t i c e f f e c t s b e c o m e i m p o r t a n t . We m u s t
m o d i f y the t h e o r y to have a reasonable approximation to r e l a t i v i s t i c theory
N, N
h
=Z i 4 <71>
i =1 i >j
quasi-relativistic Dirac Breit
The exact solution f o r HB , will again be
p
r e l RHF T
S T + x ' e l + Xff 1
XINT (72)
R e l a t i v i s t i c c o r r e c t i o n s c a n b e c o m p a r a b l e to c o r r e l a t i o n c o r r e c t i o n s
f o r a t o m s with Z S 10. So t h e e n e r g y m u s t b e s u b d i v i d e d a s :
E = E + E
rel r e l HF r e l CORR
F o r l i g h t e r a t o m s we c u s t o m a r i l y a s s u m e
E E
r e l . correlation ~ correlation (74)
and
E = E + E E
R H F C0RR+ rel (+ E
radiative corrections) ( 7 5
)
T h e r e a r e i m p o r t a n t r a d i a t i v e e f f e c t s w h i c h w e do not r e a l l y know
h o w t o h a n d l e y e t . T h e r e l a t i v i s t i c a r e a m a y b e the t h i r d p h a s e in the
a t o m i c - s t r u c t u r e t h e o r y . (The f i r s t p h a s e was the H a r t r e e - F o c k one,
t h e s e c o n d p h a s e t h e n o n - r e l a t i v i s t i c c o r r e l a t i o n , b o t h of w h i c h a r e now
q u i t e w e l l w o r k e d out. )
N o w w e p a s s o v e r to f o r b i d d e n t r a n s i t i o n s w h i c h h a v e a l o n g l i f e t i m e
s o t h a t a t o m s in a b e a m w o u l d h a v e t o t r a v e l a t l e a s t 108 t i m e s l o n g e r
b e f o r e r a d i a t i n g . In t h i s c a s e t h e b e a m - f o i l m e t h o d i s not u s a b l e .
IAEA - S M R - 1 2 / 5 2 83
New e x p e r i m e n t s f o r f o r b i d d e n l i f e t i m e s c a p a b l e of b e t t e r than f a c t o r -
o f - t w o a c c u r a c y w e r e a c c o m p l i s h e d only v e r y r e c e n t l y .
F o r b i d d e n t r a n s i t i o n s a r e i m p o r t a n t in a s t r o p h y s i c s and a t m o s p h e r i c
p h y s i c s . So one h a s to r e l y on t h e o r e t i c a l v a l u e s a s f e w e x p e r i m e n t s a r e
p o s s i b l e so f a r .
F o r b i d d e n t r a n s i t i o n s [17] (e. g. [ О I]). T h e r e i s a line (E2) a t
X = 5577 A; t h i s i s the f a m o u s oxygen g r e e n line a s o b s e r v e d in the a u r o r a .
T h i s t r a n s i t i o n i s f o r b i d d e n by the s e l e c t i o n r u l e s b e c a u s e they belong to
the s a m e c o n f i g u r a t i o n so t h a t E l i s not p o s s i b l e . It i s c a u s e d p r i m a r i l y
b y E 2 , the e l e c t r i c q u a d r u p o l e t r a n s i t i o n . O t h e r l i n e s a r e c a u s e d by
m a g n e t i c dipole (Ml) (or M l and E2) t r a n s i t i o n s so we would h a v e to c o n -
s i d e r s p i n - o r b i t coupling, e t c . f o r t h o s e l i n e s .
A c t u a l l y , H . F . - c a l c u l a t i o n s of q u a d r u p o l e t r a n s i t i o n s h a v e a s m a l l e r
e r r o r b e c a u s e of the n a t u r e of t h e o p e r a t o r . T h e d i f f e r e n c e with c o r r e l a t e d
f u n c t i o n s i s 20-30%. In o u r N C M E T , the new a t o m i c - s t r u c t u r e - t h e o r y
c a l c u l a t i o n s h a v e y i e l d e d the only a c c u r a t e r e s u l t s a v a i l a b l e in t h i s f i e l d .
T h e r e s u l t s a g r e e v e r y well with two r e c e n t e x p e r i m e n t s . A s to t h e s e
r e s u l t s we r e f e r to the r e a d e r our r e c e n t p a p e r s [18].
T h e study of the a u r o r a , w h e r e s o l a r - e m i s s i o n e l e c t r o n s e x c i t e oxygen
which r e r a d i a t e s at night, y i e l d s i n f o r m a t i o n on the e l e c t r o n d i s t r i b u t i o n
in the u p p e r a t m o s p h e r e .
Some s t u d i e s of s o l a r f o r b i d d e n and allowed t r a n s i t i o n s to t e s t
a b u n d a n c e s h a v e led to c e r t a i n d i s c r e p a n c i e s . With P . W e s t h a u s and
C. N i c o l a i d e s O. Sinanoglu h a v e m a d e c a l c u l a t i o n s with t h e new a c c u r a t e
M E T - v a l u e s of f o r b i d d e n - t r a n s i t i o n p r o b a b i l i t i e s m o d i f y i n g s o m e abundance
v a l u e s in t h e sun.
6. M O L E C U L A R BINDING AND P O T E N T I A L E N E R G Y CURVES
O r b i t a l t h e o r i e s p r e d i c t no f o r m a t i o n of F 2 f r o m two f l u o r i n e a t o m s
and no v a n - d e r - W a a l s a t t r a c t i o n s even b e t w e e n He a t o m s . T h u s , c a l c u l a t i o n s
of m o l e c u l a r e x c i t e d s t a t e g e o m e t r i e s , l i f e - t i m e s , e x c i t a t i o n e n e r g i e s ,
p o t e n t i a l e n e r g y c u r v e s on s u r f a c e s f o r ground and e x c i t e d s t a t e s , including
the m i n i m a , i . e . d i s s o c i a t i o n (De) o r a t o m i z a t i o n e n e r g i e s ( - Д Е а ) , a l l
require a non-closed-shell many-electron theory.
T h e binding e n e r g y Л Е а of, say,
A + В + С -> (ABC); Л Е а (76)
r i g o r o u s l y c o n s i s t s of a " H a r t r e e - F o c k (MO) b i n d i n g " , AE RHF and a

"correlation binding", ДЕСШК,
Д Е а = ДЕ„нг + AE CORR (7 7)
where for each species, e . g . (ABC)
E
" -ERHF + ECORR (78)
84 SINAN OG LU
with t h e e x a c t e l e c t r o n i c , a d i a b a t i c w a v e f u n c t i o n
=
^ ^RHF"1" x
CORR (79)
X = 0
^ ^RHF I CORR^
T o give an i d e a of the r e l a t i v e m a g n i t u d e s of t h e two k i n d s of c o n -

t r i b u t i o n t o m o l e c u l a r b i n d i n g , we c o m p i l e d in T a b l e s IV and V,
Д Е с о к к / Л Е а (exp), t h e b i n d i n g r a t i o , f o r a wide v a r i e t y of m o l e c u l e s . T h e
A E c o r r v a l u e s h a v e b e e n obtained u s i n g o u r c o r r e l a t i o n t h e o r y (ground
s t a t e v e r s i o n , M E T [7]) and a r e c e n t m e t h o d d e v e l o p e d b y P a m u k and
Sinaňoglu [19] which u s e s a s input the s i m p l e L C A O MO c o e f f i c i e n t s and
a t o m i c d a t a . We s e e t h a t in the g r o u n d s t a t e s t h e c o r r e l a t i o n b i n d i n g i s
t y p i c a l l y 30-40%, b u t i n c r e a s i n g to 200% (two h u n d r e d p e r cent!) in
d i a t o m i c m o l e c u l e s l i k e F 2 . T h e e f f e c t should b e even l a r g e r f o r e x c i t e d
states.
P o t e n t i a l - e n e r g y - c u r v e c a l c u l a t i o n s h a v e b e e n a t t e m p t e d in the
l i t e r a t u r e f o r s o m e t i m e . F i r s t , t h e H a r t r e e - F o c k MO m e t h o d w a s u s e d .
It i s , h o w e v e r , w e l l - k n o w n now t h a t t h e m e t h o d y i e l d s p o o r b i n d i n g and
i m p r o p e r d i s s o c i a t i o n . T h e l a t t e r i s due to t h e o v e r l o o k e d n e c e s s i t y of
t r e a t i n g even the g r o u n d s t a t e s of m o l e c u l e s a s n o n - c l o s e d s h e l l s y s t e m s
(see below). The difficulty has been o v e r c o m e by mixing a few configurations
f r o m t h e v a l e n c e s h e l l (in H 2 , log + lcr^). Thus the n e x t c a l c u l a t i o n
m e t h o d e m p l o y e d in t h e p a s t t e n y e a r s in t h e l i t e r a t u r e h a s b e e n to do
H a r t r e e - F o c k c a l c u l a t i o n s with t h e f i r s t f e w v a l e n c e - s h e l l c o n f i g u r a t i o n s
T A B L E IV. BINDING E N E R G I E S (ATOMS -> M O L E C U L E S ) O F S M A L L

P O L Y A T O M I C M O L E C U L E S - RATIO OF C O R R E L A T I O N BINDING T O
H A R T R E E - F O C K MO BINDING - P R E D I C T E D BINDING B A S E D ON
C O R R E L A T I O N T H E O R Y C O M P A R E D WITH E X P E R I M E N T (eV)
b
В. E.H. F. B E
- 'CORRB В. E. .. ,
predicted
Molecule B Е B. E.C
(H.F. МО) - - С ORR В Е (MET-EPCE-F 2 O) exp
- - exp
HCN 8. 89 4.48 33. vk 13. 6 13. 54
H20 6.77 2. 73 27. Vh 9. 6 10. 08
C02 11. 39 5.36 31. №h 16.8 16. 86
N20 3.97 6.57 56.0% 10. 5 11.73
C2N2 13.01 8.29 38. \°k 21.4 21.75
CH4 13.87 4. 34 23. 9fy 18.2 18. 18
C 2 H4 17.63 6.86 28. Vjo 24.5 24. 37
FCC H 11. 91 5.45 < 30 4

- %ED. 17.9 -
a
From various sources; references in (b).
b
O. Sinanoglu and H. Ö. Pamuk, Ref. [ 19].
c
Based on G. Herzberg, "Infrared and Raman Spectra", Van Nostrand, N . Y . (1945).
IAEA - S M R - 1 2 / 5 2 85
T A B L E V. BINDING E N E R G I E S (В. E . ; eV) (ATOMIZATION ENERGIES)

OF SIZABLE P O L Y A T O M I C S - CONTRIBUTION OF C O R R E L A T I O N T O
BINDING AND P R E D I C T I O N OF В. Е . WITH T H E T H E O R Y M E T - E P C E - F 2 c r
B E,
' C0RR
Molecule R F a
B.E.b
• CORR exp B. E. <*>' predicted
exp
Pyrrole 0. 6182 1. 7 7 6 34.8% 1.78
Pyridine 0.7233 2. 0 5 35.2% 2 . 09
Pyrazine 0.6911 1.9 36. 4% 2 . 00
Benzene 0.7530 2.24 33. 5% 2. 17
Naphthalene 1.193 3.47 34. 3<Уо 3.44
a
O. S i n a n o g l u and H. Ö. P a m u k , Ref. [ 1 9 ] .
b F r o m v a r i o u s s o u r c e s i n d i c a t e d in Ref. [ 1 9 ] .
t o g e t h e r ( m u l t i - c o n f i g u r a t i o n a l MO SCF = M C S C F , OVC, etc. ). But t h i s

t o o p r o v e s i n a d e q u a t e to obtain m o s t of the binding and the P . E . curve.
T h e following s c h e m e i l l u s t r a t e s t h i s f o r the F 2 m o l e c u l e w h e r e the b e s t
e f f o r t s by Wahl and D a s [20] and o t h e r s yielded about 30% of the D e . One
d i f f i c u l t y i s to d e c i d e how to c h o o s e the new c o n f i g u r a t i o n s .
De f o r m o l e c u l e , by d i f f e r e n t m e t h o d s
a
F2 D e (exp. ) = 1.68 eV
D e (M О SCF ; H . F . ) = -1.37 e V b
D e (MCSCF; OVC) ~ 0.6 eV°
D e (including the n o n - c l o s e d » 1.5 eV d
s h e l l new N C M E T c o r r e l a t i o n
effects, p a r t i c u l a r l y the s e m i -
internal correlation)
A s y s t e m a t i c a n s w e r i s p r o v i d e d by the r i g o r o u s N C M E T which, a s
we showed a b o v e , g i v e s t h e c o r r e l a t i o n e f f e c t s
*ЕХАСТ= ^RHF4" X
INT + + X
U
with a l l p a r t s m u t u a l l y o r t h o g o n a l .
F i g u r e 2 d e m o n s t r a t e s t h e s e e f f e c t s . T h e s e p a r t s of ¥ a r e f u l l y
s p e c i f i e d , once the i n i t i a l d o m i n a n t o r b i t a l s in the s i m p l e MO o r VB
p i c t u r e a r e s p e c i f i e d to c o n s t i t u t e the finite H a r t r e e - F o c k set o r " s e a " .
* I C Z K O W S K I , R. , MARGRAVE, J. , c f . (d) of T a b l e I .
WAHL. A . C . , J. C h e m . Phys. 4 1 , ( 1 9 6 4 ) 2 6 0 0 .
Ref. [ 2 0 ] i n t e x t ,
c f . R e f s [ 2 1 , 22] a n d [ 2 4 ] i n t e x t .
86 SINANOGLU
(Mj-Uij)
occ'd unocc'd
H.F. H.F.
NO'S MO's
J V
"CHARGE WAVE F U N C T I O N OF N C M E T " = Ф с = « R H F • X | N T • XSEM,_INT (CLOSED-SHELL-LIKE
CORRELATIONS NEEDED
(YIELDS LIFETIMES, HFS-CONSTANTS, DIPOLE MOMENTS, ETC.)
M A I N L Y FOR E N E R G Y
PROPERTIES )
FIG. 2. N e w c o r r e l a t i o n e f f e c t s in m o l e c u l e s g i v e n b y t h e N C M E T t h e o r y . ipexact- «RHF + X

C0RR;
>
<®RHf!xC0RR = о e^p-non-closed-shell Hartree-Fock M O wf "H.F. sea" = {ki} = { l o g , lo|, lo",... lir|}.
In m o l e c u l e s c o n s i s t i n g of H, B , C, N, O, and F , the
' H . F . s e t " ={ki} = -j и { l s a , 2s a , 2 p J (80)

all
i. e. the K, L spin o r b i t a l s of e a c h c o n s t i t u e n t a t o m . Or, equivalently,
H . F . s e t = {k;} = {1 Og, l o u , 2 o g , . . . 1тг§} (81)
occupied o r u n o c c u p i e d К and v a l e n c e s h e l l M O ' s (given in E q . (81) f o r

linear molecules).
In t h e n o n - c l o s e d s h e l l <ŘRHF and XINT- i n t e r n a l c o r r e l a t i o n , we have
a l l d e t e r m i n a n t s (dets), Д к , m a d e up of only t h e s e H . F . spin o r b i t a l s ,
M in n u m b e r . T h e t o t a l n u m b e r of p o s s i b l e d e t s a r e then f o r an
N-electron state.
О
0RHF + X
INT - У (82)
k= 1
T h e p r e v i o u s M C S C F (OVC, etc. ) included s o m e d e t s f r o m E q . (82).
T h e new e f f e c t found f i r s t f o r a t o m s , in N C M E T [1], is x F = s e m i -
i n t e r n a l c o r r e l a t i o n s (Fig. 2). H e r e e l e c t r o n s m a d e v i r t u a l t r a n s i t i o n s ,
s o m e within the H. F . s e t , but s o m e to new " s e m i - i n t e r n a l o r b i t a l s " , f,
beyond the f o r m e r . T h a t i s ,
k j k j -> k j fjj.
with
< f | k m > = 0 for all 1 s km s M

IAEA - S M R - 1 2 / 5 2 87
M o s t of t h e s e m i - i n t e r n a l M O ' s (dictated by s y m m e t r y ) a r e of the

o, it, 6, ф t y p e s , e. g. in l i n e a r m o l e c u l e s (made of A O ' s t h a t a r e of r o u g h l y
n = 3 r a d i a l b e h a v i o u r ) . In a single s e c o n d - r o w a t o m like С o r O, the
s e m i - i n t e r n a l Orbitals w e r e a s we s a w , 3*s, 3*p, 3*d and at m o s t
4 * f - l i k e l l ] . T h e d i s s o c i a t i o n b e h a v i o u r of t h e s e new t y p e s of M O ' s i n d i c a t e
t h e i r r e l a t i v e i m p o r t a n c e in m o l e c u l e f o r m a t i o n .
T h e l a s t e f f e c t in the e x a c t -p i s t h e " a l l - e x t e r n a l c o r r e l a t i o n " wave
f u n c t i o n х и . In the c o n f i g u r a t i o n - i n t e r a c t i o n (CI)-language it c o n s i s t s of
a l l d e t s , none of which include a n y v i r t u a l H . F . M O ' s o r A O ' s to which
t r a n s i t i o n s f r o m ф к н р h a v e taken p l a c e . Note that in the c l o s e d - s h e l l l i m i t
of a s y s t e m
^rhf ^ A 0 (single det)
\F -» 0
so that
^closed shell = Д 0 + Xu (83)
T h u s х и a r e c l o s e d - s h e l l - l i k e c o r r e l a t i o n s , t r e a t e d a s such by the c l o s e d -
s h e l l c o r r e l a t i o n t h e o r y , M E T [7], which showed the d o m i n a n c e of M O -
p a i r c o r r e l a t i o n s ûy and ey . T h e s e N ( N - l ) / 2 decoupled М О - p a i r c o r r e -
l a t i o n s , Cjj, f o r N - e l e c t r o n s i n g l e - d e t s t a t e s r e - i n t r o d u c e d in 1959-1962
with the g r o u n d s t a t e c o r r e l a t i o n t h e o r y , M E T [7] h a v e now b e e n studied
by m a n y a u t h o r s , notably K u t z e l n i g g , D a v i d s o n , C i z e k , P a l d u s , S c h a e f e r ,
K e s t n e r , King, Stanton, S t e i n e r , L a b z o w s k i , B r o w n , Roby, and o t h e r s ,
a s w e l l a s in the continuing w o r k of our own l a b o r a t o r y , f o r m a n y s m a l l
m o l e c u l e s , n o n - e m p i r i c a l l y a s w e l l a s s e m i - e m p i r i c a l l y . T h e e^- c o n -
s t i t u t e a quite a d e q u a t e way of a c c o u n t i n g f o r m o s t of the a l l - e x t e r n a l
c o r r e l a t i o n e n e r g y . How they o c c u r in n o n - c l o s e d s h e l l s t a t e s i s given
by N C M E T [1].
7. T H E S E M I - I N T E R N A L C O R R E L A T I O N E F F E C T AND M O L E C U L A R
POTENTIAL ENERGY CURVES
A s m e n t i o n e d above, the ( H . F . ) M O ' s did not yield p r o p e r P . E .

c u r v e s f o r m o l e c u l e s . T h e i n c l u s i o n of s o m e v a l e n c e c o n f i g u r a t i o n s ,
though i m p r o v i n g m a t t e r s c o n s i d e r a b l y , s t i l l did not a c c o u n t f o r m u c h of
the binding and e x c i t e d - s t a t e p r o p e r t i e s . H o w e v e r , a f t e r the s e m i - i n t e r n a l
e f f e c t w a s t h e o r e t i c a l l y found and shown to yield q u a n t i t a t i v e a t o m i c
p r o p e r t i e s , it w a s s u g g e s t e d t h a t it should be i n c l u d e d in m o l e c u l a r c a l -
c u l a t i o n s [21]. Indeed, upon i t s i n c l u s i o n , even p a r t i a l l y , f o r the f i r s t
t i m e an a d e q u a t e F 2 D e could be obtained [22]. It a l s o yielded o t h e r
m o l e c u l a r P . E . c u r v e s f o r s o m e ground and e x c i t e d d i a t o m i c s [23]. T h e
wave f u n c t i o n c a l c u l a t e d and i n c l u d i n g the c o r r e c t q u a l i t a t i v e f e a t u r e s of
P . E . s u r f a c e s , i s what we c a l l e d f o r s h o r t t h e " c h a r g e wave f u n c t i o n "
'ř c of N C M E T [24],
^c - $RHF+ XiNT+ Xf (84)

SINANOGLU
R (Ä)
1
FIG. 3. P o t e n t i a l e n e r g y c u r v e of I + BeO. T h e lower c u r v e is based on t h e N C M E T t h e o r y of
O. S i n a n o g l u (Refs [ 1, 21, 2 4 ] in t e x t ) as c a l c u l a t e d by H. F. S c h a e f e r , J. C h e m . Phys. 55, ( 1 9 7 1 ) 176.
T w o e x a m p l e s of P . E . c u r v e s a r e c o m p a r e d with e x p e r i m e n t in F i g s 3
a n d 4 w h e r e the t h e o r e t i c a l o n e s a r e o b t a i n e d with N C M E T . T o g e t m o r e
q u a n t i t a t i v e r e s u l t s , t h e a l l - e x t e r n a l c o r r e l a t i o n e n e r g y Д Е и can b e
o b t a i n e d b y t h e n e w l y d e v e l o p e d s e m i - e m p i r i c a l m e t h o d [19] and a d d e d
to the c h a r g e wave function r e s u l t
Л Е Л Е Л Е
(Р.Е.) = с + и <85)
One m a y a l s o n o t e t h e l i m i t of t h i s e q u a t i o n f o r a t r u e c l o s e d - s h e l l
s y s t e m in w h i c h , h o w e v e r and t h e r e f o r e , one c a n h a v e no c h e m i c a l binding:
t h e He - - H e , A r - - A r , e t c . n o n - b i n d i n g v a n - d e r - W a a l s c u r v e s . H e r e
( a s in E q . (83)),
ДЕ С -> A E r h f ( s i n g l e - d e t H . F . ' s ) (86)

IAEA - S M R - 1 2 / 5 2 89
2.0
FIG. 4 . P o t e n t i a l c u r v e of X 3 I ~ of 0 2 . T h e m i d d l e c u r v e is b a s e d on t h e c h a r g e w a v e f u n c t i o n of t h e N C M E T
t h e o r y by O. S i n a n o g l u (Refs [ 1, 21, 2 4 ] in t e x t ) as i m p l e m e n t e d for 0 2 by H. F. S c h a e f e r , J. C h e m . Phys.
54 ( 1 9 7 1 ) 2 2 0 7 .
and
Л Е A E Л Е
(Р.Е.) • RHF+ и <87>
He - - He,
Ar -- Ar,
etc. v a n - d e r - W a a l s i n t e r a c t i o n s
F u r t h e r m o r e , it w a s found s o m e t i m e ago that [25]
AE RHF (R) « v a n - d e r - W a a l s r e p u l s i o n s
9 A E r (R)
( v d W - r e p u l s i o n f o r c e Frep = - ^ ^ (88)
f o r a l l i n t e r n u c l e a r d i s t a n c e s , R. We h a v e in the l i m i t of l a r g e R,
AEjjfR) ^ v a n - d e r - W a a l s a t t r a c t i o n s
ЭДЕИ (R)
(89)
3R
lim AERHF-> 0
and
-С
lim ДЕ П -> —
U
R- » R6
90 SINANOGLU
H o w e v e r , the M E T [7] and N C M E T [1], yield t h e s e v a n - d e r - W a a l s f o r c e s

f o r a l l R without a s s u m p t i o n s of n o - o v e r l a p , e t c . The a p p l i c a t i o n s of the
M E T t h e o r y [7] to v a n - d e r - W a a l s f o r c e s h a v e b e e n t r e a t e d in d e t a i l in the
r e c e n t book by M a r g e n a u and K e s t n e r [26].'
We s e e f r o m E q . (12) that, f o r a p o l y a t o m i c s y s t e m with c h e m i c a l
f o r c e s ( n o n - c l o s e d s h e l l a t o m s ) , c h e m i c a l binding e f f e c t s a r e in ДЕ С ,
while ДЕц i s a g e n e r a l i z a t i o n of the v a n - d e r - W a a l s f o r c e concept even to .
the a t o m s of an individual m o l e c u l e .
T h e l o n g - r a n g e and s h o r t - r a n g e p a r t s of i n t e r m o l e c u l a r f o r c e s u s u a l l y
w e r e c a l c u l a t e d in the old l i t e r a t u r e a s s e p a r a t e p r o b l e m s ; but the p r o b l e m
h a d r e m a i n e d of how to join s m o o t h l y t h e s e two p a r t s in the i n t e r m e d i a t e
r e g i o n of the i n t e r m o l e c u l a r potential. T h i s w a s an o u t s t a n d i n g p r o b l e m
r e f e r r e d to in m o s t t e x t b o o k s , f o r which no solution had e x i s t e d . Now
with the above r i g o r o u s n o n - c l o s e d s h e l l m a n y - e l e c t r o n f o r m u l a t i o n , the
a n s w e r t o t h e P . E . c u r v e t r e a t e d in i t s e n t i r e t y f r o m R = 0 to R -» °o i s
p r o v i d e d . We showed above that both s h o r t - r a n g e and l o n g - r a n g e f o r c e s
r e s u l t f r o m t h e s a m e r i g o r o u s t h e o r y which a l s o c o m b i n e s the c h e m i c a l
f o r c e s (ДЕ С ) with t h e v a n - d e r - W a a l s a t t r a c t i o n s ( Д Е и ) .
8. THE CHARGE WAVE FUNCTION AND CHARGE DISTRIBUTION

R E L A T E D P R O P E R T I E S OF M O L E C U L A R E X C I T E D STATES
The p o r t i o n f c of t h e e x a c t wave f u n c t i o n У we called the c h a r g e wave

f u n c t i o n b e c a u s e it i s the p a r t t h a t a f f e c t s the e l e c t r o n i c c h a r g e d i s t r i b u t i o n
s i g n i f i c a n t l y , w h i l e , a s we d e m o n s t r a t e d f o r a t o m s , t h e a l l - e x t e r n a l х и
h a s l i t t l e e f f e c t e x c e p t on e n e r g y [1, 7, 24]. A s a r e s u l t , p r o p e r t i e s of
m o l e c u l a r s t a t e s r e l a t e d to c h a r g e d i s t r i b u t i o n , such a s t h e s t a t i c (dipole,
q u a d r u p o l e , . . . ) m o m e n t s , spin d e n s i t i e s , h y p e r f i n e c o n s t a n t s , including
t h e n u c l e a r q u a d r u p o l e coupling c o n s t a n t , a s well a s the s i m i l a r t r a n s i t i o n
m o m e n t s giving r i s e to e l e c t r i c dipole and q u a d r u p o l e t r a n s i t i o n p r o b a b i l i t i e s ,
a r e given by the c h a r g e wave f u n c t i o n s ¥ c . Although such p r o p e r t i e s h a v e
now b e e n e x h a u s t i v e l y studied and obtained f o r m a n y a t o m s [ l ] , a n a l o g o u s
(and j u s t a s f e a s i b l e ) a u t o m a t e d c o m p u t a t i o n s on m o l e c u l e s have j u s t begun.
REFERENCES
[1] SINANOGLU, 0 . , A t o m i c Physics V o l l , P l e n u m Press, N e w York ( 1 9 6 9 ) 131, and r e f e r e n c e s t o his e a r l i e r

papers c o n t a i n e d t h e r e i n .
[2] WESTHAUS, P . , SINANOGLU, O. , Phys. Rev. 183 (1969) 5 6 .
[3] SINANOGLU, O . , BECK, D. R . , T h e o r . C h i m . A c t a 34 ( 1 9 7 4 ) 183; Phys. Rev. L e t t . 28 (1972) 9 4 5 .
[4] SINANOGLU, O. , J. M o l . S t r u c t . , (Proc. Int. C o n f . on M o l e c u l a r S p e c t r o s c o p y , S p e c i a l Issue)
W r o c l a w , P o l a n d , 19A ( 1 9 7 2 ) 81.
[5] SINANOGLU, O . , C o m m e n t s A t . M o l . Phys. I l l (1971) 53.
[6] SINANOGLU, O . , Rev. M o d . Phys. 3 5 (1963) 5 1 7 .
[7] SINANOGLU, O . , A d v . C h e m . Phys. VI (1964) 3 1 5 .
18] MOSHINSKY, M. , NOVARO, O . , CALLES, A . , J. Phys. (Paris) 3 1 C 4 ( 1970) 125.
[9] CALLES, A . , MOSHINSKY, M . , NOVARO, 0 . , SINANOGLU, O . , Phys. L e t t . 40A ( 1972) 79.
[10] KELLY, H . P . , Phys. Rev. Д 6 B896 (1964); 144 (1966) 39.
[11] MA, S . K . , BRUECKNER, K. A. , Phys. Rev. 2 6 5 (1968) 18.
[12] CHACON, E. , MOSHINSKY, M. , NOVARO, O. , WULFMAN, C . , Phys. Rev. A 3 ( 1 9 7 1 ) 166.
[13] ALPER, J . S . , SINANOGLU, O. , Phys. Rev. 177 ( 1 9 6 9 ) 77.
[14] SINANOGLU, O. , S K U T N I K , В . , C h e m . Phys. L e t t . 1 ( 1 9 6 8 ) 6 9 9 .
IAEA - S M R - 1 2 / 5 2 91
[15] WEISS, A . W , , Phys. Rev. 162 ( 1 9 6 7 ) 71.

[16] BASHKIN, S . , B e a m - F o i l S p e c t r o s c o p y , G o r d o n and B r e a c h , N e w York ( 1 9 6 8 ) .
[17] SINANOGLU. O. , C o m m e n t s A t . M o l . Phys. j l (1970) 7 9 .
[18] a) SINANOGLU, O . , N u c l . I n s t m r n . M e t h o d s , Proc. T h i r d I n t . BFS C o n f . 110 (1973) 193.
b ) SINANOGLU, O . , C o m m e n t s A t . M o l . Phys. 2 N o . 3 ( 1 9 7 0 ) 7 9 ;
NICOLAIDES, C . A . , SINANOGLU, O . , WESTHAUS, P . , Phys. Rev. A 4 ( 1 9 7 1 ) 1400.
[19] SINANOGLU, O . , PAMUK, H. Ö . , T h e o r . C h i m . A c t a 27 ( 1 9 7 2 ) 2 8 9 ; J. A m . C h e m . S o c . 9 5 ( 1973) 5 4 3 5 .
[20] WAHL, A . C . , DAS, G . , J. C h e m . Phys. £ 7 (1967) 2 9 3 4 .
[21] SINANOGLU, O . , C o m m e n t s A t . M o l . Phys. I l l (1971) 5 3 and e a r l i e r r e m a r k s .
[22] DAS, G . , WAHL, A . C . , Phys. Rev. L e t t . 2 4 (1970) 4 4 0 ; WAHL, A . C . , GILBERT, T . C . ,
SINANOGLU, O. e t al. , I n t . J. Q u . C h e m . Ills (1969) 4 7 9 .
[23] SCHAEFER, H . , J. C h e m . Phys. _55 ( 1 9 7 1 ) 176.
[24] BECK, D . , NICOLAIDES, C . , LUKEN, W . , SINANOÖLU, O . , I n t . J. Q u a n t . C h e m . _VIs( 1972) 1,
[25] KESTNER, N . R . , SINANOGLU, O . , J. C h e m . Phys. 4 5 ( 1 9 6 6 ) 194.
[26] MARGEN A U , H . , KESTNER, N . R . , T h e o r y of I n t e i m o l e c u l a r F o r c e s , 2nd Edn, P e r g a m o n Press,
London ( 1 9 7 1 ) .
IAEA-SMR-12/4, 5
O B S E R V E D S T R U C T U R E O F ATOMIC S P E C T R A
B. EDLÉN
Institute of Physics,
University of Lund,
Lund, Sweden
Abstract
OBSERVED STRUCTURE OF ATOMIC SPECTRA .

1. T h e c e n t r a l - f i e l d m o d e l of t h e a t o m ; 1 . 1 . Nucleus plus o n e e l e c t r o n ; 1.2. Closed shells plus o n e
e l e c t r o n (Rydberg series, i s o - e l e c t r o n i c sequences); 1 . 3 . Closed shells plus two electrons; 2. Series limits
and i o n i z a t i o n energies; 2 . 1 . T h e Ritz formula; 2 . 2 . T h e p o l a r i z a t i o n f o r m u l a ; 2 . 3 . I o n i z a t i o n energies
as functions of Z and N; 3 . Level intervals in i s o - e l e c t r o n i c sequences; 3 . 1 . " E l e c t r o s t a t i c " intervals;
3 . 2 . S p i n - o r b i t intervals; 3 . 3 . W a v e numbers of transitions; 4 . Survey of e l e c t r o n configurations and t e r m
systems; 4 . 1 . Ground configurations in t h e first half of the p e r i o d i c system (structure of 2 - to 1 0 - e l e c t r o n
systems, 1 1 - to 1 8 - e l e c t r o n systems, N = 1 9 - 2 8 , 3dk configurations); 4 . 2 . Ground configurations for N==47
4 . 3 . Brief survey of l i t e r a t u r e .
1. THE C E N T R A L - F I E L D MODEL OF THE ATOM
To d e s c r i b e t h e s y s t e m c o r e p l u s e l e c t r o n (n, t ) w e u s e t h e f o l l o w i n g
d e f i n i t i o n s : Z = n u c l e a r c h a r g e ; N = t o t a l n u m b e r of e l e c t r o n s ; Z - N = s t a g e
of i o n i z a t i o n ; Z - (N - 1) = Ç, t h e n e t c h a r g e of t h e c o r e = s p e c t r u m " n u m b e r "
f H, He + , L i 2 + , . . . Л
VH I, He II, L i III, . . . У
1.1. N u c l e u s p l u s one e l e c t r o n
T h e b i n d i n g e n e r g y i s g i v e n by
T =RZ2/n2; n = 1, 2, 3, . . . (1)
1. 2. C l o s e d s h e l l s p l u s one e l e c t r o n
D e g e n e r a c y in I i s r e m o v e d by p e n e t r a t i o n and i s q u a l i t a t i v e l y e x p l a i n e d
by e l l i p t i c o r b i t s . T h e b i n d i n g e n e r g y in t h e l i m i t of n e g l i g i b l e p e n e t r a t i o n i s
T = R Г 2 /п 2 (2)
D e p a r t u r e s f r o m (2) a r e e x p r e s s i b l e in two w a y s :
(a) T =RÇ2/(n-6)2 (3)
w h e r e n - ó = n* i s t h e e f f e c t i v e q u a n t u m n u m b e r and б i s t h e q u a n t u m d e f e c t ;
it d e p e n d s on SL but i s a p p r o x i m a t e l y i n d e p e n d e n t of n; h e n c e t h e g e n e r a l
f o r m u l a for a Rydberg s e r i e s is obtained.
93
94 EDLEN
FIG. 1 . I s o e l e c t r o n i c r e l a t i o n s for Li I a n d Na I l i k e s p e c t r a . A g a i n s t Z a r e p l o t t e d ( f r o m t o p to b o t t o m ) :
t h e " r e d u c e d " t e r m v a l u e t = T / R Ç 2 = ( n * ) " 2 ; V T / R = £ / n * = (£ + p ) / n , i l l u s t r a t i n g M o s e l e y ' s l a w ; t h e p e n e t r a t i o n
p = nVT7Ř"-S; from Ref.[11].
IAEA-SMR-12/4, 5 95
T A B L E I. C O M P L E T E F O R M U L A S FOR pf AND p g IN T H E P A I R -
C O U P L I N G A P P R O X I M A T I O N ( f r o m Ref. [ I l l )
Limit Designation
Config. Relative energy
J L К I
li G (4i) 5,4 +k p + 5F 2
li G <3i) 4,3
1 - f e p - 5 F 2 ± У ( Й р - 5 Е , ) 2 + Т5рг
i F (3i )' 4,3
pf .
li D (2i) 3,2
} -4Cp-fF2±y(ICp-iF/+180F2
i F (2i)' 3,2
li D (li) 2,1 + kp+12F2
r li H (5Í) 6,5 + Í C p + 28F 2
li H (4i) 5,4
i -iSp-¥F 2 W(Í5p-¥F2) + 2 1 5 6 F2
ii G (4Í)' 5,4
pg -
li F (3i) 4,3
j -ií p - 1 1 F Z ± 7 ( | i ; p - l l F 2 ) 2 + 4 2 3 5 F*
i G (3i)' 4,3
li F (2i) 3,2 + Í C p + 55F2
T A B L E II. F O R M U L A S F O R p 6 f , p 5 g , d 9 f , AND d 9 g IN P U R E P A I R
C O U P L I N G ( f r o m R e f . [11])
Parent Pair Pair
Relative energy Relative energy
level symbol symbol
Configuration p5f Configuration p5g
(3i)' + CP (4ÍV
r P
(2i)' H p (3i)" H p
i
(4i) - k p - 5F 2 (5i) " i c p - 28F 2
! (34) -kp+10F2 (4i) -Í£p+49F2

РзА
(2i) -kp+ 3F 2 (3i) -i£p+22F2
-
(li) - k p - 12F 2 (2i) -iCp-55F2
9
Configuration d f Configuration d 9 g
+
(4i)' +fcd- 7F 2 (5i)- f£d-39;F 2
(3i)' + 14F 2 (4i)' + fCd+68|F2
(2i)' +fcd +
4*F 2 (3i)> + f£d+30|F2
+
- (li)' |Cd-16jF2 (2i) ' +
fcd- "f2
(5i) - Cd" "F, (6i) - Cd- 56F 2

(4i) + 12
- Cd F2 (5i) - Cd + 5 3 i F 2
2
(3i) - Cd+ 12F
2 (4i) - £ d + 66|FZ
d5/2
(2i) - Cd+ rFz (3i) - Cd+23|F2
13
(li) - Cd" iF2 (2i) - Cd " « !
(i) - С d ~ 2 4 F2 di) - Sd " 1 1 0 F í
96 EDLEN
(b)
T = R(Ç+p)2/n® (4)
w h e r e Ç + p i s t h e e f f e c t i v e c h a r g e and p i s t h e p e n e t r a t i o n ; p d e p e n d s o n n
a n d JL but i s a p p r o x i m a t e l y i n d e p e n d e n t of Ç; it i s s u i t e d f o r i s o e l e c t r o n i c
comparison.
Ç+p = Z - s , s is called the s c r e e n i n g p a r a m e t e r .
F i g u r e 1 s h o w s t h e Z - d e p e n d e n c e of T / R and t h a t
(1) T / R Ç 2 = (n*)" 2 t e n d s t o w a r d t h e h y d r o g e n i c v a l u e .
(2) N/T/R= (Ç + p ) / n i s l i n e a r in Z ( M o s e l e y ' s law).
(3) n ^ T / R - Ç = p i s a p p r o a c h i n g a c o n s t a n t v a l u e .
1. 3. C l o s e d s h e l l s p l u s two e l e c t r o n s
T o t h e c e n t r a l - f i e l d - e n e r g y i s a d d e d t h e m u t u a l i n t e r a c t i o n e n e r g y of
t h e two e l e c t r o n s : t h e C o u l o m b e n e r g y , e x p r e s s e d by S l a t e r ' s F k , -
e x c h a n g e e n e r g y , e x p r e s s e d by S l a t e r ' s G k , and t h e m a g n e t i c i n t e r a c t i o n
e n e r g y of t h e o r b i t a l (SL) and s p i n (s) a n g u l a r m o m e n t a of e a c h e l e c t r o n ,
e x p r e s s e d by the p a r a m e t e r Ç n i .
The four angular m o m e n t a s b i 2 , s 2 , c o u p l e to t h e t o t a l a n g u l a r
m o m e n t u m J . C o u p l i n g i s p e r f o r m e d in s t e p s a r r a n g e d to give m e a n i n g f u l
i n t e r m e d i a t e r e s u l t a n t s . F o u r c a s e s of c o u p l i n g a r e p o s s i b l e :
(1) L S : (jř^í2)(sis2) LS - J ( e l e c t r o s t a t i c coupling)
(2) j j : ( í 1 s 1 ) ( í 2 s 2 ) - j g 2 - J ( m a g n e t i c coupling)
(3) jK: ( i l S l ) i 2 s2 - (j!Í2)s2 - K s 2 - J I „ „ C0UDling
Р&1Г C0U
(4) LK: ( M 2 ) Sl s 2 - (L Sl ) s 2 - KS2 - J J Pllng
H\SL<1 a r e c o u p l e d by C o u l o m b f o r c e s ,
SjS 2 a r e c o u p l e d by e x c h a n g e f o r c e s ,
m a g n e t i c c o u p l i n g of ( i j i 2 ), ( s ^ ) , ( í ^ ) , ( í 2 Sj) i s n e g l i g i b l e . D a t a and
r e l a t i o n s c o n c e r n i n g p a i r - c o u p l i n g a r e c o m p i l e d in T a b l e s I and II.
M
'P 'P, +/
+a„ 1n
/
/
/
/
S
/ electro- spin- magnetic
P / static orbit field
\
\
\\
\
\
4
-г
-èr
3
P<
\ 3p
I con fig. 2 terms h levels 12 states
FIG.2. T h e o r e t i c a l p i c t u r e of a n s p - c o n f i g u r a t i o n in d i f f e r e n t a p p r o x i m a t i o n s ; f r o m R e f . [ 1 1 ] .
IAEA-SMR-12/4, 5 97
JJ
v —
FIG.3. G r a p h i c r e p r e s e n t a t i o n of t h e l e v e l s t r u c t u r e for t h e c o n f i g u r a t i o n s sp a n d sp 5 in i n t e r m e d i a t e c o u p l i n g ;
from Ref.[ll].
785 r~
aos 0.Ю DJS

Fz/t, Ш0/Т13
F I G . 4 . Structure of pf In i n t e r m e d i a t e coupling in t h e p a i r - c o u p l i n g FIG. 5. Structure of 2 p 5 nf in N e I showing pure pair c o u p l i n g ( s e e
a p p r o x i m a t i o n a c c o r d i n g to the formulas in T a b l e I ( a f t e r K . B . Eriksson, T a b l e II), t h e straight lines represent the t h e o r e t i c a l structure, from Ref.f 11],
Ref.[11]).
IAEA-SMR-12/4, 5 99
T h e L S - c o u p l i n g of s p , LS-*jj f o r sp a n d s p 5 , a s w e l l a s L K - c o u p l i n g
f o r 2p nf in N II and j K - c o u p l i n g f o r 2 p 5 nf in N e I a r e i l l u s t r a t e d in F i g s 2 - 5 .
F o r f u r t h e r i n f o r m a t i o n , we m a y r e f e r to t h e a r t i c l e " A t o m i c S p e c t r a "
in H a n d b . d e r P h y s i k , Vol. XXVII, S p r i n g e r - V e r l a g , B e r l i n (1964), and a l s o
" C o u p l i n g c o n s i d e r a t i o n s in t w o - e l e c t r o n s p e c t r a " by R. D. C o w a n and
K. L . A n d r e w , p u b l i s h e d in J . Opt. Soc. A m . _55 (1965), a s w e l l a s R e f . [2].
2. S E R I E S L I M I T S AND IONIZATION E N E R G I E S
2.1. The Ritz f o r m u l a
Let us f i r s t give the definitions:
E n - level e n e r g y counted u p w a r d s f r o m the ground level;

E
i i m = e n e r g y of s e r i e s l i m i t on t h e s a m e s c a l e ;
T n = E U m - E n = i o n i z a t i o n e n e r g y of t h e l e v e l E n , and t n = T n / R Ç 2 = ( n - 6 ) " 2
When w r i t i n g
Tn = R Ç 2 / ( n - 6 ) 2 (5)
we find 6 t o b e n e a r l y l i n e a r in T :
6n = a + b t n (6)
T a b l e III and F i g . 6 d e m o n s t r a t e t h i s r e l a t i o n s h i p (the R i t z f o r m u l a )
f o r a t e r m s e r i e s in Al III. T h e s l o p e (sign of b) i s p o s i t i v e f o r t h e
" p e n e t r a t i n g o r b i t s " n s and np, n e g a t i v e f o r t h e " n o n - p e n e t r a t i n g "
T A B L E III. AI III, R I T Z F O R M U L A S ( f r o m I S B E R G , B. , A r k . F y s . 35
(1968) 561)
n s 2 S i / 2 : = 0.8948072 + 0 . 1 1 6 6 4 7 t + 0.062977 t 2 ;
n p 2 P i / 2 : = 0.5897972 +0.186943 t + 0.18388 t 2 +0.11721 t 3 ;
np2P3/2: = 0.5881677 +0.188183 t+0.17540 t2 +0.14607 t 3 ;
nd2D: = 0.0736909 - 0 . 1 7 8 4 2 4 t - 0.23931 t 2 .
T
obs"Tcalc . cm"1
n
2 2 2
Si/Z Pф *P3/2 D
3 (0) (0) (0) (0)
4 (0) (0) (0) (0)
5 (0) (0) (0) (0)
6 0.04 (0) (0) 0.00
7 -0.04 -0.08 -0.05 -0.02
8 -0.09
100 EDLEN
FIG. 6 . Ritz d i a g r a m of t h e t e r m s e r i e s in AI III ( a f t e r В. I s b e r g , A r k . Fys. 3 5 ( 1 9 6 8 ) 5 6 1 ) .
nd, nf, e t c . To account f o r d e v i a t i o n s f r o m l i n e a r i t y t h e R i t z f o r m u l a

m a y be e x p a n d e d :
б n = a + bt n +ctl+.
n .. v(7)
'
The s e r i e s l i m i t is d e t e r m i n e d by v a r y i n g t h e v a l u e of E l i m until t h e Ritz

l i n e s p r o p e r l y a p p r o a c h l i n e a r i t y with i n c r e a s i n g n.
F o r a t o m i c s y s t e m s with m o r e t h a n one e l e c t r o n o u t s i d e c l o s e d s h e l l s
t h e R i t z l i n e s a r e o f t e n d i s t o r t e d by p e r t u r b i n g t e r m s , T 0 , which do not
belong to the s e r i e s but h a v e t h e s a m e p r o p e r t i e s (parity, J and o t h e r valid
IAEA-SMR-12/4, 5 101
q u a n t u m n u m b e r s ) a s t h e s e r i e s t e r m s Tn . The d e v i a t i o n s can be t a k e n
into account by adding to t h e Ritz e x p r e s s i o n a t e r m a / ( T n - T 0 ) with the sign
c o r r e s p o n d i n g to r e p u l s i o n b e t w e e n T 0 and T n . The e f f e c t i s due to m a t r i x
c o m p o n e n t s c o n n e c t i n g d i f f e r e n t c o n f i g u r a t i o n s . Such c o n f i g u r a t i o n i n t e r -
a c t i o n s a r e v e r y c o m m o n . F i g u r e s 7, 8 and 9 show s o m e e x a m p l e s .
2. 2. The p o l a r i z a t i o n f o r m u l a
The R i t z d i a g r a m f o r AI III s h o w s f o r nf, ng and nh a s t r i k i n g r e g u l a r i t y

in t h e Í - d e p e n d e n c e of 6. F o r t h e s e s t r i c t l y n o n - p e n e t r a t i n g o r b i t s t h e
i n c r e a s e in binding e n e r g y o v e r the h y d r o g e n i c v a l u e T H i s due a l m o s t
e n t i r e l y to a p o l a r i z a t i o n of t h e c o r e in the f i e l d of t h e o u t e r e l e c t r o n :
Л
Р = Т
" Т
н ="dR<r"4> (8)
102 EDLEN
FIG. 8 . P e r t u r b e d series in Si III ( a f t e r Y . T o r e s s o n , A r k . Fys. 18 (1960) 4 1 2 ) . (a) P e r t u r b a t i o n of t h e

s e r i e s 3 s n f 3 F 4 a n d !F 3 by t h e l e v e l s 3 p 3 d 3 F 4 a n d ' F 3 . (b) P e r t u r b a t i o n in t h e series 3 s n d . The perturbing
t e r m 3p2 ID 2 is s i t u a t e d a t T = 141.9 k K .
H e r e • \ r " 4 / i s an a v e r a g e v a l u e of r ~ 4 ; r i s the r a d i u s of t h e e l e c t r o n ' s

o r b i t in u n i t s of a 0 , and o-j is t h e dipole p o l a r i z a b i l i t y of t h e a t o m i c c o r e
F o r an o u t e r e l e c t r o n with the q u a n t u m n u m b e r s n and i t h e
theory gives
/ -4 \ _ «4 3 n 2 - 1 ( 1 + 1)
' 2n5(s>-D-eu+lm + D(i +1)
A c c o r d i n g to E q s (8) and (9) a single p a r a m e t e r , o?d , would d e t e r m i n e T f o r

any o r b i t n i with SL s u f f i c i e n t l y l a r g e . To extend t h e validity r a n g e of the
f o r m u l a we m a y include q u a d r u p o l e p o l a r i z a t i o n :
Др = a d R < r - 4 > + * q R < r - 6 > (10)

IAEA-SMR-12/4, 5 103
•к
FIG.9. P e r t u r b e d series in C a I ( a f t e r G . Risberg, A r k . Fys. 37 (1968) 2 4 4 ) / (a) n - n * versus l e v e l v a l u e

for t h e 4sns s e r i e s , (b) n - n * versus l e v e l v a l u e for t h e 4snp 3 P 2 a n d i P j s e r i e s .
104 EDLEN
T A B L E IV. AI III, T H E POLARIZATION FORMULA; C A L C U L A T E D AND

OBSERVED VALUES O F Д р FOR T H E H Y D R O G E N - L I K E TERMS ( f r o m
IS BERG, В . , A r k . F y s . 35 (1968) 560)
Д р = 20.510 P ( n , l ) [1 + 12.710 q(n, 1)].
Term Ap(calc) Ap (obs) A p (obs)-

TH,cm"i T
c a l c • с™"1
symbol cm-1 cm"i Ap (calc)
4f 61726.709 105.90 105.90 (0) 61832.61
5f 2 F 39 505.142 64.29 64.29 (0) 39 5 6 9 . 4 3
6f 2 F 27 4 3 4 . 1 2 2 40.43 40.43 0.00 27 4 7 4 . 5 5

2
7f F 20 1 5 5 . 6 6 9 26.70 26.79 0.09 20 1 8 2 . 3 7
8f 2 F 15431.673 18.43 18.56 0.13 15450.10
9f 2 F 12 1 9 2 . 9 1 8 13.21 13.48 0.27 12 2 0 6 . 1 3

2
5g G 39 504.903 12.21 12.21 (0) 39 5 1 7 . 1 1
6g2G 27 4 3 3 . 9 8 3 8.00 8.15 0.. 15 27 4 4 1 . 9 8
7g2G 20 155.582 5.40 5.60 0.20 20 1 6 0 . 9 8

2
8g G 15431.615 3.77 3.87 0.10 15 4 3 5 . 3 9
9g2G 12 1 9 2 . 8 7 7 2.72 2.66 -0.06 12 1 9 5 . 6 0

2
6h H 27 4 3 3 . 8 9 5 2.40 2.10 -0.29 27436.29
7h2H 20 1 5 5 . 5 2 6 1.68 1.72 0.05 20 1 5 7 . 2 0
8h2H 15 4 3 1 . 5 7 7 1.20 1.20 0.01 15 4 3 2 . 7 7

2
9h H 12 1 9 2 . 8 5 1 0.87 0.70 -0.П 12 1 9 3 . 7 3
71 e I 20155.487 0.63 20 1 5 6 . 1 2
8i 2 I 15431.551 0.46 15 4 3 2 . 0 2
2
9i I 12 1 9 2 . 8 3 3 0.35 12 1 9 3 . 1 8
8k 2 K 15431.532 0.20 15431.73

2
9k K 12 1 9 2 . 8 1 9 0.15 12 1 9 2 . 9 7
2
9i L 12 1 9 2 . 8 0 9 0.07 12 1 9 2 . 8 8
w h e r e o-q is in u n i t s of a§ and < ^ r - 6 ) i s given by an e x p r e s s i o n in n and S.

a n a l o g o u s to (9). If (10) is w r i t t e n a s
Ap/P(n,J>)=A + Bq(n,i) (11)
P and q being t a b u l a t e d f u n c t i o n s of n and I , and o b s e r v e d v a l u e s of Д р / Р

a r e plotted a g a i n s t q, they should f a l l on a s t r a i g h t line f r o m which t h e
p a r a m e t e r s A ( c o r r e s p o n d i n g to a<j ) and В ( c o r r e s p o n d i n g to o q ) a r e
d i r e c t l y obtained (see also T a b l e IV). F i g u r e 10 s h o w s this plot f o r AI III,
and F i g . 11 f o r В III, С IV, N V.
IAEA-SMR-12/4, 5 105
FIG. 10. G r a p h i c i l l u s t r a t i o n of t h e p o l a r i z a t i o n f o r m u l a a p p l i e d t o AI III. I n d i c a t e d error l i m i t s c o r r e s p o n d

to i 0 . 1 5 c m " ' in Д р ( a f t e r B . I s b e r g , A r k . Fys. 3 5 (1968) 5 6 0 ) .
2. 3. Ionization e n e r g i e s a s f u n c t i o n s of Z and N
By u s e of the Ritz and the p o l a r i z a t i o n f o r m u l a s a c c u r a t e v a l u e s f o r

i o n i z a t i o n e n e r g i e s h a v e b e e n d e r i v e d f o r m a n y a t o m s and ions. F o r o n e -
and t w o - e l e c t r o n s y s t e m s (H- and H e - l i k e ) t h e o r e t i c a l c a l c u l a t i o n s s u r p a s s
o r c o m p e t e in a c c u r a c y with e x p e r i m e n t a l v a l u e s . In t h e s e c o n d p e r i o d
(N = 3 - 10) e x p e r i m e n t a l ionization e n e r g i e s a r e now s u f f i c i e n t l y a c c u r a t e
and c o m p l e t e to p e r m i t an i n t e r e s t i n g study of t h e i r d e p e n d e n c e on Z at
c o n s t a n t N ( i s o - e l e c t r o n i c s e q u e n c e ) and on N at c o n s t a n t We adopt
the f o r m :
T = Rn'2 [ ? 2 + a Ç + b + c ( Ç + d ) - 1 ] + A r (12)
w h e r e a i s t a k e n f r o m t h e o r y , b, с and d a r e a d j u s t e d to fit o b s e r v a t i o n s ,
and Л r r e p r e s e n t s the r e l a t i v i s t i c c o n t r i b u t i o n . In T a b l e s V and VI the
r e s u l t s a r e c o m p i l e d f o r N = 3 ( l s 2 2 s ) and N = 4 ( I s 2 2 s 2 ) ; s e e a l s o F i g . 12.
F o r t h e s y s t e m s l s 2 2 s 2 2 p k (k= 1 - 6 ) t h e i o n i z a t i o n p o t e n t i a l s T c w e r e
t a k e n a s the e n e r g y d i f f e r e n c e b e t w e e n c e n t r e s of g r a v i t y of ground
c o n f i g u r a t i o n s of c o n s e c u t i v e i o n s . Then all p a r a m e t e r s b e c o m e s m o o t h
106 EDLEN
0 0.10 0.20 0.30 q(nl)
FIG. 11. Д р / P í n S ) as a f u n c t i o n of q ( n í ) for В III, С IV a n d N V. T h e lines for С IV a n d N V a r e based o n

t h e o r e t i c a l v a l u e s of A a n d o b s e r v e d v a l u e s of Ap(3d) ( a f t e r A . Ö l m e , A r k . Fys. 4 0 (1969) 4 3 ) .
T A B L E V. IONIZATION ENERGY O F I s 2 2s ( f r o m R e f . [12])
T(obs), c m " 1 V RM/4 6(calc)b T(calc) c
He" 0 27 4 3 0 . 5 7 -0.02481 -680
Li I 43 4 8 7 . 1 3.2 27 4 3 2 . 1 6 -0.23242 43 4 8 7 . 1
ВеП 146 8 8 2 . 9 ± 0.3 21.8 27 4 3 2 . 6 6 -0.28161 146 8 8 2 . 9
В in 305931.1± 0.6 79.3 27 4 3 2 . 9 4 -0.30363 305 930.7
С IV 520 1 7 8 . 4 ± 1.5 209.8 27 4 3 3 . 0 7 -0.31612 520 1 7 9 . 6
N V 7 8 9 537 ± 3 458.6 27 4 3 3 . 2 5 -0.32416 789 5 3 8 . 6
О VI 1 114008 ilO 882.1 27 4 3 3 . 3 9 -0.32978 1 1 1 4 008
F VII 1547.2 27 4 3 3 . 5 3 -0.33392 1 4 9 3 629
N e VIII 2532.1 27 4 3 3 . 5 8 -0.33710 1 9 2 8 462
a 4
Дг = 0.4565(5+0.63) cm-i, w h e r e 0 . 4 5 6 5 = -|rRc(2 •
b
6 = -0.361344+0.20899ÍC +0.621)-!.
c
T=(RM/4)fe2 + 0 . 8 1 7 5 6 £ + 0 ) + A r i w h e r e 0 . 81756 = 4 - 8 A e t w i t h Д С 1 f r o m t h e o r y .
IAEA-SMR-12/4, 5 107
T A B L E VI. IONIZATION E N E R G Y O F l s 2 2 s 2 ( f r o m R e f . [12])

a
С T(obs),cm_1 6(calc)b T(calc)c
Li" 0 0.18755 5 145
Bel 1 75 1 9 2 . l è 0 . 1 10.7 0.03233 75192.1
В II 2 202 8 8 7 . 4 è 0 . 8 47.9 - 0.02248 202 8 8 7 . 4
С III 3 3 86 2 4 1 . 0 ± 2 142.0 -0.05051 386241.5
N IV 4 6 2 4 866 ±3 333.8 -0.06753 624 8 6 4 . 6
O V 5 918657 ±4 674.5 - 0.07896 918 6 5 8 . 5
F VI 6 1226.8 - 0.08716 1 267 622
N e VII 7 2063.9 - 0.09334 1 6 7 1 792
a
Д г =0.4565(C + 1 . 2 0 ) « c m - i , where 0.4565 = - | r R a 2 .
b
6 = - 0 . 1 3 7 1 6 8 + 0 . 3 5 4 5 9 f e + 1. 092) - l .
c
T=(RM/4)fe2 + 1.70825c+6) + Д г , where 1.70825 = 6 - 8Де! withÄCj from theory.
f u n c t i o n s of k, and Д г i s s i g n i f i c a n t l y r e d u c e d and m a y b e p r o v i s i o n a l l y
n e g l e c t e d . T h e d e p e n d e n c e of T c on к and on Ç i s shown in F i g . 13 and
T a b l e VII.
We w i s h t o c o m p a r e t h e e m p i r i c a l r e l a t i o n s with r e s u l t s of s e c o n d -
o r d e r p e r t u r b a t i o n c a l c u l a t i o n s e x p r e s s e d in t h e f o r m
E(N) = E q (N)Z 2 + E 1 ( N ) Z +E2(N) (13)
w h e r e E(N) i s t h e t o t a l e n e r g y of t h e N - e l e c t r o n s y s t e m . If we put
A E j ( N ) = Ej(N) - E j ( N - 1) (14)
and i n t r o d u c e t h e v a l u e f o r E 0 ( N ) , we get f r o m (13) t h e i o n i z a t i o n p o t e n t i a l s

(in H a r t r e e u n i t s ) :
- AE(N) = (2n 2 )" 1 [(Z 2 - 2 n 2 A E 1 ( N ) Z - 2n 2 AE 2 (N)] (15)
C o m p a r i s o n of E q . (15) with t h e e m p i r i c a l e x p r e s s i o n (12) a f t e r r e p l a c e -

m e n t of Ç by Z - (N - 1) g i v e s :
a=2(N-l)-2n2AE1(N) (16)
- A E 2 ( N ) = ( N - 1) A E j Í N ) - [(N - l) 2 - b ] (2П 2 )" 1 (17)
H e r e n= 2. By a d o p t i n g t h e known t h e o r e t i c a l v a l u e f o r Д Е : and i n t r o d u c i n g
t h e e m p i r i c a l l y d e r i v e d b in E q . (17) we o b t a i n an e x p e r i m e n t a l v a l u e of Д Е 2 .
S i n c e t h e H a r t r e e - F o c k v a l u e s A E 2 F a r e e x a c t l y known we can e x p r e s s t h e
r e s u l t s in t e r m s of t h e c o r r e l a t i o n e n e r g y
AE",r = A E 2 - A E f (18)
The c o m p a r i s o n of e x p e r i m e n t a l and t h e o r e t i c a l v a l u e s f o r ДЕ 2 0 Г Г
in F i g . 14 r e v e a l s t h e p r e s e n t u n c e r t a i n t y in t h e t h e o r y .
1 0 8 EDLEN
FIG. 12. T h e quantities ó = ( T - A r ) r f / R M + a Ç ) p l o t t e d a g a i n s t С = Z - (N - 1); f r o m R e f . [ 1 2 ] .
3. L E V E L INTERVALS IN I S O - E L E C T R O N I C SEQUENCES
3. 1. "Electrostatic" intervals
F r o m the f a c t t h a t t h e p e n e t r a t i o n p a r a m e t e r p in the e x p r e s s i o n f o r
binding e n e r g i e s
T = R(Ç + p ) 2 / n 2
r e m a i n s r o u g h l y c o n s t a n t when Ç v a r i e s , it f o l l o w s t h a t i n t e r v a l s b e t w e e n
l e v e l s with e q u a l n a r e a p p r o x i m a t e l y l i n e a r in Z (or Ç) and t h o s e
IAEA-SMR-12/4, 5 109
1 2 3 4 5 6
40
39
38
i 37
36
35
34
СИ N11 ОП F II Nell Nail
FIG. 13. T h e d e p e n d e n c e on к of t h e i o n i z a t i o n p o t e n t i a l s T a n d T c of 2s2 2 p k f o r £ = 2 ; f r o m R e f . [ 1 2 ] .
c o r r e s p o n d i n g to d i f f e r e n t n a r e q u a d r a t i c in Z (or f ) . T h u s , by dividing
t h e i n t e r v a l s by a l i n e a r f u n c t i o n , Ç + a, one o b t a i n s in t h e f i r s t c a s e an
a p p r o x i m a t e l y c o n s t a n t value and in t h e s e c o n d c a s e a l i n e a r function.
T h i s is t h e s i m p l e b a s i s f o r t h e i s o - e l e c t r o n i c c o m p a r i s o n of e l e c t r o s t a t i c
energy intervals.
It f o l l o w s a l s o t h a t binding e n e r g i e s tend t o w a r d t h e i r h y d r o g e n i c v a l u e s
s i n c e , with i n c r e a s i n g t h e quotient (Ç + p)/Ç a p p r o a c h e s unity.
The c h a n g e s with Ç in t h e r e l a t i v e p o s i t i o n s of c o n f i g u r a t i o n s having
d i f f e r e n t c o m b i n a t i o n s of n - v a l u e s a r e well i l l u s t r a t e d in the Ca I s e q u e n c e
a s shown in F i g . 15. The l o w - l y i n g c o n f i g u r a t i o n s a r e in t u r n (4s4s), (4s3d)
and (3d3d). All l i n e s r e p r e s e n t i n g a given c o m b i n a t i o n of (n, n) a r e p a r a l l e l .
Such a g r o u p is b e s t s t u d i e d by t a k i n g one of the l e v e l s of t h e g r o u p as
r e f e r e n c e l e v e l , a s shown in F i g . 16 f o r 3 d 2 . Note i r r e g u l a r i t i e s in t h e
beginning of t h e s e q u e n c e , due to c o n f i g u r a t i o n i n t e r a c t i o n when t e r m s
f r o m different configurations r e v e r s e their relative positions as Ç changes.
The d i a g r a m in F i g . 17 f o r the t e r m s of 2s3£ and 2p3ü in t h e Be I s e q u e n c e
s h o w s a s i m i l a r b e h a v i o u r , f i r s t s o m e i r r e g u l a r i t i e s and then a p e r f e c t l y
s m o o t h a s y m p t o t i c Ç - d e p e n d e n c e . T h i s i s a v e r y i m p o r t a n t aid in t h e
p r a c t i c a l a n a l y s i s of s p e c t r a , e s p e c i a l l y f o r high i o n i z a t i o n s t a g e s .
3. 2. Spin-orbit intervals
In t h e h y d r o g e n i c e x p r e s s i o n f o r t h e s p i n - o r b i t e n e r g y p a r a m e t e r
D 2 Z„ 4
_ Rtt
-
nai(í +1)
we r e p l a c e Z by a " s c r e e n e d " c h a r g e , Z - s, and f i n d t h a t s p i n - o r b i t i n t e r v a l s

should v a r y a s (Z - s) 4 with s a p p r o x i m a t e l y c o n s t a n t . A f i n e e x a m p l e i s t h e
110 EDLEN
T A B L E VII. IONIZATION ENERGIES T c (cm" 1 ) F O R CONFIGURATION

C E N T R E S O F I s 2 2 s 2 2 p k ( f r o m Ref. [ 12])
Spectrum Tc(obs) 6(calc)a Tc(calc)b T-T c
2s 2 2 p
ВI 66 918 -0.41474 66 918 10
С II 196 622 -0.54087 196 622 42
N III 3 8 2 588 -0.61618 3 8 2 588 116
О IV 6 2 4 125 -0.66624 6 2 4 115 257
F V -0.70192 920 904 496

г
2s* 2р
С I 86004 -0.33472 86 0 0 4 4 816
N II 231529 -0.49983 231529 7 222
0 III 433 583 - 0.60440 4 3 3 583 9 504
F IV -0.67656 691394 11736
Ne V -0.72936 1004604 13 938
2sz 2p3
N I 106 2 9 8 -0,20765 106 2 9 8 10 928
0 II (267 467) -0.41519 267 467 15787
F III 485491 - 0.55030 485491 2 0 287
N e IV -0.64527 759484 ( 2 4 506)
Na V -0,71567 1 0 8 9 020 2 8 603

z
2s 2p4
О I 127 797 -0,03423 127 797 - 17 960
F II 3 0 4 525 -0.28486 3 0 4 525 -22466
N e III (538416) - 0.45184 538416 ( - 2 6 797)
Na IV -0.57105 828486 -31109
Mg V -0.66043 1174242 -35155
2S2 2p5
F I 150 4 4 3 0.18285 150 4 4 3 - 9918
N e II 342 649 -0.11200 3 4 2 649 - 12 260
Na III (592297) -0.31302 5 9 2 297 - 14 584
M g IV -0.45885 8 9 8 327 - 16 895
Al V - 0.56948 1 2 6 0 191 - 19249

2
2s 2p6
Ne I 174190 0.44138 174190 - 260
Na II 381850 0.10278 3 8 1 850 -455
M g III 647 152 -0.13471 647 152 -743
A l IV -0.31050 969 014 - 1 148
Si V -0.44587 1 3 4 6 854 -1698

IAEA-SMR-12/4, 5 111
N O T E S T O TABLE VII
a
Ó = T c / 2 7 4 3 4 ~ ( £ 2 + a £ ) , w h e r e a = 2(N - 1) - 8 Д £ 1 , w i t h f r o m t h e o r y and 2 7 4 3 4 = R / 4 .
k T c ( c a l c ) from t h e following formulas with 3 adjusted parameters:
2s 2p : T c / 2 7 4 3 4 = £ 2 + 1 . 8 5 3 9 8 t - 0 . 9 1 4 7 2 + 1 . 4 8 1 9 4 ( ç + 1. 9 6 4 Г 1
2
2s22p2: T c / 2 7 434 = £2 + 2 . 4 6 9 6 6 £ - 1 . 0 7 0 1 3 + 2 . 5 4 0 1 ( Ç + 2 . 4 5 4 ) " 1

2s 2 2 p 3 : T c / 2 7 4 3 4 = £2 + 3 . 0 8 2 3 3 ? - 1 . 1 8 9 5 3 + 3 . 6 6 3 4 (C+2.731)-1
2 s 2 2 p 4 ; T c / 2 7 4 3 4 = £ 2 + 3 . 69257C - 1 . 2 8 5 3 8 + 4 . 9946 (Ç+2.992)"1
2s 2 2p5 ; T c / 2 7 4 3 4 = £ 2 + 4 . 3 0 0 9 7 C - 1 . 3 7 5 4 2 + 6 . 6 7 7 2 fe+3.285)"1
2 s2 2p 6 : T c / 2 7 4 3 4 = £ 2 + 4 . 9 0 8 0 4 Ç - 1 . 4 8 7 9 5 + 9 . 0640 (£ + 3 . 6 9 8 ) " *
™ (N ^ <N <N (NI <N

l/> V> U) 1 Л 1 Л 1 Л 1 Л 1 Л
C N t N ^ ( N f v j C M f N C M
FIG. 14. C o m p a r i s o n of t h e o r e t i c a l a n d e x p e r i m e n t a l values of Д Е 2 ° Г Г = Л Е 2 - Д Е Р ' ' . Curve A calculated

by K n i g h t ( 1 9 6 9 ) ; C u r v e В d e r i v e d o b s e r v a t i o n s by using from s e m i - e m p i r i c a l f o r m u l a s g i v e n by Edlen in R e f . [12];
C u r v e С c a l c u l a t e d by S a f r o n o v a a n d I v a n o v a ( 1 9 6 9 ) .
112 EDLEN
FIG. 15. S u r v e y d i a g r a m of t h e m a i n c o n f i g u r a t i o n s i n C a I - l i k e s p e c t r a . S e r i e s l i m i t s a r e i n d i c a t e d by
dashed lines; from Ref.[11].
FIG. 16. L e v e l s of 3d^ in C a I - l i k e s p e c t r a . T h e ' S l e v e l , w h i c h falls h i g h a b o v e t h e rest of t h e c o n f i g u r a t i o n ,

has b e e n o m i t t e d ; f r o m R e f . [ 1 1 ] .
IAEA-SMR-12/4, 5 113
г-ptà 'P
i-p 3 i ' F
2s3tL 'D
L-грзр 'D
lS3p 'P
-Ь грзр 'P
FIG. 17. I s o e l e c t r o n i c c o m p a r i s o n of t h e t e r m s of 2 s 3 i a n d 2 p 3 i in Be I - l i k e s p e c t r a . Д Е - E - 2s3d 1 D o r

E - 2s3d 3 D; AL = 0 f o r 2 s 3 i and ÄL = 2p2p - 2s 2 S for 2 p 3 i ; f r o m R e f . [ l l ] .
114 EDLEN
(Z-S)"1
0.18 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.0
FIG. 18. G r a p h i e r e p r e s e n t a t i o n of t h e s p i n - o r b i t i n t e r v a l 2 s 2 2 p S ( 2 P 1 / 2 - 2 р з / г ' - T h e v a l u e s m a r k e d by c i r c l e s

a r e o b t a i n e d f r o m f o r b i d d e n t r a n s i t i o n s o b s e r v e d in t h e solar c o r o n a , t h o s e m a r k e d by crosses a r e f r o m
-
laboratory observations. T h e s i z e of t h e i n t e r v a l i n c r e a s e s f r o m 4 0 4 c m ' i n F I t o 30 0 4 5 c m " ' i n C a XII;
f r o m Ref. [ 1 4 ] .
g r o u n d - t e r m i n t e r v a l , 2 P i / 2 " 2 Р з / г in t h e F I s e q u e n c e s h o w n in F i g . 18.
H e r e the s c r e e n i n g p a r a m e t e r s is plotted against ( Z - s ) " 1 , producing a
straight line.
T h e i n t e r v a l s in t h e g r o u n d c o n f i g u r a t i o n s 2 s 2 2 p k (k = 1 - 5 ) and 3 s 2 3 p k
a r e of s p e c i a l a s t r o p h y s i c a l i n t e r e s t a s h o l d i n g t h e c l u e t o t h e " f o r b i d d e n "
l i n e s in t h e g a s e o u s n e b u l a e and the s o l a r c o r o n a . A c c o r d i n g l y , t h e i r
Z - d e p e n d e n c e h a s b e e n m u c h s t u d i e d . F i g u r e 19 s h o w s two of t h e
i n t e r v a l s of 2 s 2 2p 4 in t h e О I s e q u e n c e , X D 2 - 3 P X and 3 Р г - 3 P 2 , r e p r e s e n t e d
by s t r a i g h t l i n e s o b t a i n e d by u s i n g a s u i t a b l e t r a n s f o r m a t i o n .
3.3. W a v e n u m b e r s of t r a n s i t i o n s
T h e t r a n s i t i o n s s e p a r a t e w i t h i n c r e a s i n g Ç into two d i s t i n c t g r o u p s
c o r r e s p o n d i n g t o A n = 0 (wave n u m b e r b e i n g a l i n e a r f u n c t i o n of £) and
A n / 0 (wave n u m b e r b e i n g a q u a d r a t i c f u n c t i o n of f ) . T h i s i s i l l u s t r a t e d
by t h e d i a g r a m in F i g . 20 f o r t h e Na I s e q u e n c e .
It i s i n t e r e s t i n g t o n o t e t h a t t h e v a l u e s of t h e t r a n s i t i o n p r o b a b i l i t i e s
t e n d to z e r o with i n c r e a s i n g Ç f o r A n = 0 and t o n o n - z e r o h y d r o g e n i c v a l u e s
f o r An / 0.
IAEA-SMR-12/4, 5 115
у,/у
1.0 0.9 0.8 0.7 0.6 0.5 0.3 0.2 0.1 0
( 2 , - 3 . 2 5 у ' ( 2 - 3.25)
FIG. 19. G r a p h i c r e p r e s e n t a t i o n of i n t e r v a l s in t h e g r o u n d c o n f i g u r a t i o n s 2s 2 2p 4 in t h e О I i s o e l e c t r o n i c
sequence. T h e lines labelled a n d F2 r e p r e s e n t t h e i n t e r v a l s C P j - 3 Р г ) a n d № г - з р ^ , respectively. The
design of t h e d i a g r a m is e x p l a i n e d i n R e f . [ 1 5 ] ,
4. SURVEY O F E L E C T R O N CONFIGURATIONS AND T E R M SYSTEMS
4. 1. G r o u n d c o n f i g u r a t i o n s in t h e f i r s t half of t h e p e r i o d i c s y s t e m
The g r o u n d c o n f i g u r a t i o n s of s u c c e s s i v e s t a g e s of ionization a r e
r e s p o n s i b l e f o r the l o w - l y i n g t e r m s a s well a s f o r t h e s e r i e s l i m i t s , and
t h u s d e t e r m i n e the m a i n f e a t u r e s of t h e s y s t e m s of e n e r g y l e v e l s . T a b l e VIII
shows t h e s e ground c o n f i g u r a t i o n s o r d e r e d a c c o r d i n g to t h e t o t a l n u m b e r
of e l e c t r o n s N f o r the f i r s t half of t h e p e r i o d i c s y s t e m . C l o s e d s h e l l s
a r e o m i t t e d when p a s s i n g f r o m one p e r i o d to t h e next. In t h e l a s t r o w of
e a c h p e r i o d we have given only t h e f i r s t e l e m e n t of e a c h i s o e l e c t r o n i c
s e q u e n c e , the f i g u r e in p a r e n t h e s i s being t h e n u m b e r к of equivalent
electrons.
In p e r i o d s I to III the g r o u n d c o n f i g u r a t i o n s r e m a i n t h e s a m e t h r o u g h o u t
e a c h i s o e l e c t r o n i c s e q u e n c e . On t h e o t h e r hand, in p e r i o d IVa, t h e
c o m p o s i t i o n of the ground c o n f i g u r a t i o n s c h a n g e s with i n c r e a s i n g net c h a r g e
in t h a t t h e 4 s - o r b i t s , which a r e p r e s e n t in t h e beginning of a s e q u e n c e , a r e
r e p l a c e d by 3 d - o r b i t s a s i n d i c a t e d in T a b l e VIII. T h i s t r a n s f o r m a t i o n i s
116 EDLEN
a l w a y s c o m p l e t e d in t h e t h i r d m e m b e r of e a c h s e q u e n c e and f o r the l a t t e r
p a r t of t h e p e r i o d a l r e a d y in t h e second m e m b e r . The f o l l o w i n g two p e r i o d s ,
IVb and Va, a r e in all r e s p e c t s a n a l o g o u s to III and IVa. T h e conventional
n u m b e r i n g of the p e r i o d s is c l e a r l y not t h e m o s t r a t i o n a l one f o r o u r
p u r p o s e , which h a s l e d u s to i n t r o d u c e s u b d i v i s i o n s .
(a) T w o - to t e n - e l e c t r o n s y s t e m s
A view of t h e p r e s e n t s t a t e of a n a l y s i s of s y s t e m s with up to 18 e l e c t r o n s
i s given in T a b l e IX. By u n d e r l i n i n g a s p e c t r u m s y m b o l we h a v e i n d i c a t e d
t h a t t h e a n a l y s i s i s c o m p l e t e d a s f a r a s p r a c t i c a l l y p o s s i b l e with a v a i l a b l e
l i g h t s o u r c e s . S y m b o l s a r e given in p a r e n t h e s i s f o r v e r y i n c o m p l e t e
a n a l y s e s , and an a s t e r i s k s i g n i f i e s t h a t t h e s p e c t r u m is at p r e s e n t b e i n g
investigated.
IAEA-SMR-12/4, 5 117
T A B L E VIII. GROUND CONFIGURATIONS O F ATOMS AND IONS IN T H E

F I R S T H A L F O F T H E PERIODIC SYSTEM
Period N Configuration3 Spectrum
1 Is HI, H e l l , Lilll
2 Is? Hel, Lill, Belli
3 2s L i l , Bell, Bill
2
4 2s Bel, BII, CIII
5-10 2s 2 2 p k BC1). C(2), N(3), 0 ( 4 ) , F(5), Net6)
11 3s N a l , MglI, A1III
12 3s? M g l , A1II, S i l l l
13-18 3 s2 3 p k A l ( l ) , Si(2), P(3), S(4), C K 5 ) , A K 6 )
19 4s -»3d KI, C a l l , S c I I I
20 4s 2 -»3d2 C a l , S e n , T1III, . . .
21-28 4 s 2 3 d k ' " 2 -> 3 d k S c ( 3 ) , T i ( 4 ) , V(5), C r ( 6 ) , M n ( 7 ) , Fe(8), C o ( 9 ) , Ni(10)
29 4s C u l , ZnII, G a l i i
30 4s 2 Znl, Gall, Gelll

2 k
31-36 4s 4 p G a ( l ) , G e ( 2 ) , As(3), S e ( 4 ) , Br(5), Kr(6)
37 5s -» 4d Rbl, Srll, та,...
38 5s 2 -» 4d 2 Sri, YIt, Z r l l l
k
39-46 5s24dk"- 2 - , 4 d Y ( 3 ) , Zr(4), Nb(5), M o ( 6 ) , T c ( 7 ) , Ru(8),Rh(9), P d d O )
a
T h e g r o u n d s t a t e is a c t u a l l y p r o v i d e d by 4 s 3 d 5 in CrI, by 5 s 4 d k _ 1 in N b l , M o l , Rul, RhI, a n d by
4di» in Pd I.
The t w o - e l e c t r o n s y s t e m s of t h e He s e q u e n c e a r e of s p e c i a l i n t e r e s t
f r o m the t h e o r e t i c a l point of view. T h e y a r e t h e s i m p l e s t s y s t e m s f o r
which the S c h r ö d i n g e r e q u a t i o n cannot be e x a c t l y s o l v e d and a r e , t h e r e -
f o r e , e x t e n s i v e l y u s e d f o r t e s t i n g v a r i o u s a p p r o x i m a t i o n m e t h o d s . At t h e
s a m e t i m e t h e y a r e t h e m o s t c o m p l i c a t e d s y s t e m s f o r which t h e o r e t i c a l
c a l c u l a t i o n s of the e n e r g i e s can be c a r r i e d f a r enough to c o m p e t e in
a c c u r a c y with t h e m e a s u r e m e n t s [1]. F o r h i g h e r Z t h e c a l c u l a t i o n s a r e
a c t u a l l y a h e a d of t h e o b s e r v a t i o n s . T h i s is a c h a l l e n g e to the e x p e r i m e n t e r s .
It is in the f i r s t p l a c e a q u e s t i o n of finding a d e q u a t e light s o u r c e s f o r t h e s e
hard-to-excite spectra.
T h e l o w - l y i n g c o n f i g u r a t i o n s in t h e eight s e q u e n c e s of g r o u p II c o n s i s t
of 2s and 2p e l e c t r o n s only. The t y p i c a l Z - d e p e n d e n c e of t h e r e l a t i v e
p o s i t i o n s of c o n f i g u r a t i o n s i s d e m o n s t r a t e d in F i g . 21 by t h e t e r m d i a g r a m s
f o r t h e i s o e l e c t r o n i c s p e c t r a С И, О IV and Na VII. It shows how t h e
c o n f i g u r a t i o n s 2 s 2 p 2 and 2p 3 m o v e down t h r o u g h t h e d i a g r a m and e v e n t u a l l y
f o r m with 2 s 2 2 p a w e l l s e p a r a t e d l o w - l y i n g g r o u p . This a s y m p t o t i c
a r r a n g e m e n t is r e a c h e d a l r e a d y in О IV. The t e r m s t r u c t u r e of t h e s e
118 EDLEN
T A B L E IX. S T A T E O F ANALYSIS O F SYSTEMS WITH 2 T O

18 E L E C T R O N S
Is* He I Li II Belli* (BIV) СV (N VI) .

2s Lil Bell Bill СIV NV 0 VI ,
2s2 Bel* BII* CIII NIV OV F VI *
2s2 2p В I* СП NIII* OIV F V* NeVI>;:
2
2s 2p2 CI Nil Olli* FIV * Ne V* Na VI
2s22p3 N1 Oil* Fill Ne IV* Na V Mg VI
2s2 2p4 01 F II Nelil* NaIV Mg V AlVI ,
2s2 2ps FI Nell Na III* Mg IV Al V Si VI ,
2
2s 2p6 Ne I Na II Mg III Al IV* Si V PVI .
3s Na I Mg II A1III Si IV P V* S VI
2
3s Míl A1H* Si III PIV* (SV) (Cl VI) ,
3s2 3p All Si II Pill* S IV (CIV) (Ar VI) .
3s2 3p2 Sil PII S III Cl IV (Ar V) (KVI) .
3s2 3p3 PI Sil* C1III Ar IV КV Ca VI ,
3s2 3p" SI* C1II* Ar III* К IV Ca V (Sc VI) ,
3 s2 3p5 Cli ArH К III Ca IV* (Sc V)* Ti VI .
2
3s Зрб Arl KII* Ca III Sc IV* Ti V* (v ví):
Underlined: Analysis essentially complete.

In parentheses: Analysis fragmentary.
* Work in progress.
kK
С И OIV NaVII
2s2p
2s 2p
2p
2s2p
2s1
3p
I—3s
3d В
3p 2p
В
2p>
2p3
2
2s2p
2s2p! 2s2 2p
40 2s2pz 2s'2p
• 2s'2p
50
FIG.21. S c h e m a t i c d i a g r a m s of t h e i s o e l e c t r o n i c t e r m s y s t e m s of С II, О IV and Na VII s h o w i n g t h e t r e n d

towards a h y d r o g e n i c a r r a n g e m e n t of c o n f i g u r a t i o n s w i t h i n c r e a s i n g i o n i z a t i o n .
kK
100
90
2р
80
2р'
70
60
50 2s2p6 >
S
2 s 2p 5 .2S
J
40 P
2s2p'
3
Р
30 3
D
20
2s2p
2р
l
10 P
2
D
2s 2s 2р 2s2 2р3 2s22p' 2s22p5
2
P -
Lil... NeVIII BeI...NaVIII BI...MgVIII CI...AIVUI NI...SÍVIII OI...PVIII FI...SVI1I

0 0.Í0 0.91 1.34 1.77 2.20 2.63
FIG.22. Observed term values of all configurations 2s m 2p 1 < 1 divided by (£ + a ) . where С = 1 - 8 and
a = 0 . 4 8 ( m - 1) +0.43k, m and k referring to the ground configurations. The first ionization l i m i t is indicated
by a cross.
120 EDLEN
FIG.23. T h e d o u b l e t s y s t e m of F 111. W a v e l e n g t h s of t r a n s i t i o n s g i v e n i n A ( a f t e r H , P a l e n i u s , Phys.

S c r i p t a 1 (1970) 115).
IAEA-SMR-12/4, 5 121
FIG.24, T h e t e r m s y s t e m of Mg II ( a f t e r P. Risberg, A r k . Fys. 9 (1955) 4 8 3 ) .
l o w - l y i n g c o n f i g u r a t i o n s g i v e s t h e c h a r a c t e r to t h e s p e c t r a of g r o u p II.
A s u r v e y pf t h e whole s e t i s given in F i g . 22, w h e r e t h e e n e r g y s c a l e h a s
b e e n n o r m a l i z e d by r e m o v i n g by a l i n e a r Z - d e p e n d e n c e .
The i n t e r v a l s within t h e g r o u n d c o n f i g u r a t i o n s a r e of p a r t i c u l a r
astrophysical significance. The e l e c t r o s t a t i c t e r m intervals appear as
t h e " f o r b i d d e n l i n e s " in t h e g a s e o u s nebulae, and t h e s p i n - o r b i t i n t e r v a l s ,
which i n c r e a s e with the f o u r t h p o w e r of the e f f e c t i v e c h a r g e eventually
r e a c h a s i z e s u f f i c i e n t to m a k e t h e m o b s e r v a b l e a s f o r b i d d e n l i n e s in t h e
solar corona.
The s p e c t r a in p e r i o d II a r e r e l a t i v e l y s i m p l e . The m a x i m u m
c o m p l e x i t y , o c c u r r i n g a r o u n d the m i d d l e of the p - s h e l l , is well i l l u s t r a t e d
by t h e t e r m d i a g r a m of F III shown in F i g . 23. It shows m a n y R y d b e r g
s e r i e s going to d i f f e r e n t l i m i t s , and t e r m s of h y d r o g e n i c o r b i t s up to 6h,
which p e r m i t an a c c u r a t e d e t e r m i n a t i o n of the s e r i e s l i m i t s .
FIG.25. T h e t e r m system of Si III ( a f t e r Y . Toresson, A r k . Fys. 18 (1960) 389).
IAEA-SMR-12/4, 5 123
(b) E l e v e n - to e i g h t e e n - e l e c t r o n s y s t e m s
T h e s t a t e of a n a l y s i s , in t h e t h i r d p e r i o d , IS! = 11 - 18, i s l e s s c o m p l e t e
t h a n in t h e p r e v i o u s one ( s e e T a b l e IX). T h e ground c o n f i g u r a t i o n s c o n s i s t
of 3s and 3p e l e c t r o n s only, and a r e c o m p l e t e l y a n a l o g o u s to t h o s e in
p e r i o d II. H o w e v e r , t h e 3d o r b i t h a s the s a m e p r i n c i p a l q u a n t u m n u m b e r
and m a y , t h e r e f o r e , t a k e p a r t in t h e f o r m a t i o n of t h e a s y m p t o t i c a l l y deep
c o n f i g u r a t i o n s . T h i s i n t r o d u c e s a s i g n i f i c a n t c o m p l i c a t i o n a s we s h a l l s e e .
The s o d i u m - l i k e o n e - e l e c t r o n s p e c t r u m of Mg II is a good e x a m p l e of
a c o m p l e t e a n a l y s i s . The d i a g r a m in Fig. 24 s h o w s how f a r t h e o b s e r v a t i o n s
go, but R i t z f o r m u l a s and t h e p o l a r i z a t i o n f o r m u l a d e r i v e d f r o m t h e o b s e r v e d
d a t a , t o g e t h e r p e r m i t an a c c u r a t e and u n l i m i t e d e x t r a p o l a t i o n of t h e l e v e l
system.
The addition of j u s t one m o r e e l e c t r o n i m m e d i a t e l y l e a d s to a c o n s i d e r -
able c o m p l i c a t i o n a s i s s e e n f r o m F i g . 25 which r e p r e s e n t s t h e t e r m s y s t e m
of Si III. The s i n g l e t and the t r i p l e t s y s t e m each c o n s i s t s of two s y s t e m s ,
FIG.26. O b s e r v e d t e r m s of t h e ( 3 , 3 ) c o n f i g u r a t i o n s in t h e M g I i s o e l e c t r o n i c s e q u e n c e . T h e first i o n i z a t i o n
l i m i t is i n d i c a t e d by a cross.
124 EDLEN
built on t h e l i m i t s 3 s 2 S and 3 p ž P , r e s p e c t i v e l y . H i g h e r up in t h e i s o e l e c -
t r o n i c s e q u e n c e one will have to c o n s i d e r the p o s s i b l e a p p e a r a n c e of a t h i r d
s y s t e m , built on 3d 2 D.
F i g u r e 26 is a n o r m a l i z e d i s o - e l e c t r o n i c d i s p l a y of t h e t e r m s a r i s i n g
f r o m the c o n f i g u r a t i o n s 3 s 2 , 3s3p, 3s3d, 3p 2 and 3p3d. The c o n f i g u r a t i o n s
3s3d and 3p2 o v e r l a p and have the s a m e p a r i t y , which r e s u l t s in a c o m p l e t e
c o n f i g u r a t i o n m i x i n g f o r t h e two J D l e v e l s . The o b s e r v a t i o n s f o r 3p3d a r e
i n c o m p l e t e , and the l a s t (3, 3 ) - c o n f i g u r a t i o n , 3 d 2 , h a s not yet been o b s e r v e d
in any of t h e s e s p e c t r a .
The a n a l o g o u s d i a g r a m f o r t h e t h r e e - e l e c t r o n s p e c t r a of t h e Al s e q u e n c e
i s shown in F i g . 27. The c o n f i g u r a t i o n s 3s3p 2 and 3 s 2 3d o v e r l a p and i n t e r a c t
s t r o n g l y . This is a l s o t h e c a s e with 3p 3 and 3s3p3d f o r which, h o w e v e r ,
the o b s e r v a t i o n s a r e v e r y i n c o m p l e t e . O t h e r c o n c e i v a b l e c o n f i g u r a t i o n s
with all e l e c t r o n s having n= 3 a r e 3 s 3 d 2 , 3p 2 3d, 3p3d 2 and 3d 3 . T h u s we
get a l t o g e t h e r 9 d i f f e r e n t c o n f i g u r a t i o n s of t h i s kind, which l e a d s to an
a s y m p t o t i c s t r u c t u r e f o r high Ç which will be quite c o m p l i c a t e d . The
h i g h e r o n e s of t h e s e c o n f i g u r a t i o n s will n e v e r be p r o m i n e n t in t h e s p e c t r u m ,
1 2 3 4 5 6 7 8 9 10 f
AI Si P S ci Ar К Ca Sc тГ
I II III IV V VI VII VIII IX X
FIG.27. O b s e r v e d t e r m s of c o n f i g u r a t i o n s w i t h n - 3 for a l l t h r e e e l e c t r o n s i n t h e AI I s e q u e n c e . E 0 is t h e
c e n t r e of g r a v i t y of 3s2 3 p 2 p ( a f t e r Ekberg a n d Svensson, Phys. S c r i p t a 2 (1970) 2 8 3 ) .
IAEA-SMR-12/4, 5 125
but t h e y m i g h t be e x p e c t e d to p r o d u c e a d e n s e b a c k g r o u n d of faint l i n e s in
the r e g i o n of t h e 3 s - 3 p and 3p-3d t r a n s i t i o n s . T h e c o m p l e x i t y i n c r e a s e s
a s we go up t h r o u g h t h e p e r i o d . T h e s i t u a t i o n in t h e t h i r d p e r i o d i s thus
in s h a r p c o n t r a s t to t h e p r e v i o u s p e r i o d , w h e r e t h e r e is a m a x i m u m of
t h r e e d e e p c o n f i g u r a t i o n s , e a c h one with a r e l a t i v e l y s i m p l e s t r u c t u r e
(cf. F i g . 22).
(c) N = 1 9 - 2 8 ; the c o n f i g u r a t i o n s 3 d k 4 s m
We now p a s s on to t h e next p e r i o d w h e r e 3 d - e l e c t r o n s f o r m t h e ground

c o n f i g u r a t i o n s and give t h e c h a r a c t e r to t h e s p e c t r a . T h e s u r v e y in
T a b l e X of t h e s t a t e of a n a l y s i s shows that p r e v i o u s l y empty p l a c e s f o r t h e
i m p o r t a n t t h i r d and f o u r t h s p e c t r a a r e beginning to be filled, t h a n k s to
r e c e n t w o r k e s p e c i a l l y at the Z e e m a n L a b o r a t o r y and the O p t i c a l I n s t i t u t e
in M a d r i d . The l a b e l " e s s e n t i a l l y c o m p l e t e " h a s h e r e a m e a n i n g t h a t i s
s o m e w h a t d i f f e r e n t f r o m t h a t in t h e p r e v i o u s p e r i o d s . E x c e p t f o r t h e f i r s t
few and t h e l a s t s e q u e n c e in t h i s p e r i o d , it is p r a c t i c a l l y i m p o s s i b l e to
m a k e a c o m p l e t e a n a l y s i s of m o r e than s o m e of t h e l o w e s t c o n f i g u r a t i o n s .
In t h e c a s e of high ionization s t a g e s t h e c o n f i g u r a t i o n s t h a t can be o b s e r v e d
in any d e t a i l a r e likely to be l i m i t e d to 3d k , 3d k _ 1 4 s and 3d k " 1 4p. T h e
o b s e r v a b l e s p e c t r u m will then c o n s i s t of two g r o u p s , one s h o r t - w a v e g r o u p
a r i s i n g f r o m ( 3 d - 4 p ) - t r a n s i t i o n s and one l o n g - w a v e group of ( 4 s - 4 p ) -
transitions.
As a p p e a r s f r o m F i g . 28 the m a x i m u m d e g r e e of c o m p l e x i t y i s r e p r e -
s e n t e d in s o m e of the i r o n s p e c t r a . The e x p e r i m e n t a l s i t u a t i o n m a y be
i l l u s t r a t e d by the f a c t t h a t in t h e g r o u p of ( 3 d 5 - 3 d 4 4 p ) - t r a n s i t i o n s in F e IV
t h e r e have b e e n m e a s u r e d about 500 lines- o v e r the r a n g e 500 Â to 700 Â.
T A B L E X. S T A T E O F ANALYSIS O F SYSTEMS WITH 19 TO

28 E L E C T R O N S
4s 3d KI Call S c III T i IV V V*
4s 2 -» 3d 2 Ca I Sell* T i III VIV Cr V *

2 3
4s 3d -» 3 d Sei Till VIII Cr I V * MnV
4s 2 3 d 2 — 3 d 4 Til VII * C r III МП IV Fe V
4s 2 3 d 3 - 3d5 VI C r II Mnlll Fe I V * (Co V)
4s 2 3 ď » - 3d s Cr I MnII Fe III (Co I V ) * (Ni V)
4s 2 3d 5 -* 3d' Mn I Fe II Colli Ni I V * (Си V)
4s 2 3d 6 -» 3d» Fe I Co I I * N i III C u IV (ZnV)

2 9
4s 3 d ' - 3d Col Ni II C u III * ZnIV (Ga V)
4s 2 3 d 8 -> 3 d 1 0 Nil Cull Znlll GaIV Ge V
Underlined: Analysis essentially c o m p l e t e .

In p a r e n t h e s e s : Analysis f r a g m e n t a r y or non-existent.
* Work i n progress.
126 EDLEN
40 -
к i= 1 2 3 4 5 6 7 8 9
n = 2 9 19 34 37 34 19 9 2
í VIII. VII VI V IV 111 II I 3dk
Fe < VII VI V IV III II I

(III) II I 3dk"2
FIG. 2 8 . T h e n u m b e r of l e v e l s a r i s i n g f r o m 3 d k for d i f f e r e n t v a l u e s of k .
In s o m e r e g i o n s t h e r e a r e m o r e than t e n o b s e r v e d l i n e s p e r a n g s t r o m unit,
and an i n s t r u m e n t with a l a r g e r d i s p e r s i o n ( h e r e it was 4 i / m m ) would
give s t i l l m o r e l i n e s , s i n c e m a n y of t h e o b s e r v e d o n e s r e p r e s e n t two o r
more unresolved transitions.
With i n c r e a s i n g e f f e c t i v e c h a r g e (f) the binding e n e r g y of 3d i n c r e a s e s
r e l a t i v e to t h a t of 4 s b e c a u s e of t h e d i f f e r e n c e in p r i n c i p a l quantum n u m b e r .
The c o n s e q u e n t c h a n g e s in t h e r e l a t i v e p o s i t i o n s of c o n f i g u r a t i o n s a r e d i s -
played in F i g . 29 w h e r e t h e l o w e s t t e r m in e a c h of the c o n f i g u r a t i o n s 3d k + 1
and 3 d k _ 1 4 s 2 h a s b e e n p l o t t e d a s a function of к and Ç by t a k i n g a s r e f e r e n c e
l e v e l t h e c e n t r e of g r a v i t y of the two t e r m s of 3 d k 4 s t h a t a r i s e f r o m the
lowest t e r m of 3 d k . T h e t e r m v a l u e s h a v e b e e n divided by (Ç + а), w h e r e
a= 0 . 6 + 0 . 1 k, in o r d e r to get a l i n e a r d e p e n d e n c e on f (or Z). The d a s h e d
l i n e s c o n n e c t c o r r e s p o n d i n g points f o r s u c c e s s i v e v a l u e s of к (or Z) at
c o n s t a n t f . They i l l u s t r a t e the r e l a t i o n s h i p s d i s c u s s e d in 1954 by C a t a l a n ,
R o h r l i c h and S h e n s t o n e . It is s t r i k i n g how t h e s t r u c t u r e in t h e f i r s t half
of the p e r i o d r e p e a t s i t s e l f in t h e s e c o n d half.
The d i a g r a m in F i g . 2 9 shows that in the n e u t r a l a t o m s 3 d k _ 1 4 s 2 i s in
g e n e r a l t h e l o w e s t c o n f i g u r a t i o n and 3d k + 1 i s f a i r l y high, while in the s e c o n d
s p e c t r a t h i s o r d e r is r e v e r s e d and 3 d k 4 s c o m p e t e s with 3d k + 1 in p r o v i d i n g
t h e ground s t a t e . F r o m the t h i r d s p e c t r u m on 3d k + 1 is d e f i n i t e l y the l o w e s t
c o n f i g u r a t i o n , while 3 d k _ 1 4 s 2 r u n s up high in t h e t e r m s y s t e m and e v e n -
tually d i s a p p e a r s .
A m o r e d e t a i l e d p i c t u r e of t h e t e r m s t r u c t u r e i s obtained by expanding
and c o m p l e t i n g t h e d i a g r a m s of F i g . 29 f o r individual i s o - e l e c t r o n i c
s e q u e n c e s . T h i s i s shown by t h e d i a g r a m s in F i g s 30 and 31 of t h e C a I -
and Ni I - l i k e s e q u e n c e s , which r e p r e s e n t t h e beginning and t h e end of t h e
p e r i o d . F o r f u r t h e r d e t a i l s s e e Ref. [4].
I A E A - S M R - 1 2 / 4 ,5 127
Call Selil... Sei Till VIII... VI Crll Mn II]... Mn ! Fell Colli... Col NiliCuIII... Cul Znll...
FIG. 2 9 . C o n d e n s e d v i e w of che r e l a t i v e p o s i t i o n s of t h e c o n f i g u r a t i o n s 3 d k 4 s m o b t a i n e d by p l o t t i n g
(E - E 0 )/(C + a ) , w h e r e E is t h e l o w e s t t e r m of 3 d k + 1 or ed^ - ! 4 s 2 , E 0 is t h e c e n t r e of g r a v i t y of t h e two t e r m s
of 3 d k 4 s b u i l t o n t h e l o w e s t t e r m of 3 d k , a n d a = 0 . 6 + 0 . 1 k.
T h e g r o u p s IVb and Va a r e quite analogous to t h e p r e v i o u s two g r o u p s

as we can s e e f r o m T a b l e VIII. E x c e p t f o r a c o n s i d e r a b l y i n c r e a s e d s p i n -
o r b i t s p l i t t i n g , the s p e c t r a have a r e m a r k a b l y s i m i l a r s t r u c t u r e . We s h a l l
l e a v e it at t h a t and p a s s on to a v e r y b r i e f s u r v e y of the s e c o n d half of t h e
periodic system.
4. 2. Ground c o n f i g u r a t i o n s of s y s t e m s with N ě 47
T h e s e c o n d half of t h e p e r i o d i c s y s t e m h o l d s p o s s i b i l i t i e s f o r a c o n -
s i d e r a b l e r e a r r a n g e m e n t of o r b i t s in the l o w - l y i n g c o n f i g u r a t i o n s .
A c c o r d i n g to a w e l l - k n o w n e m p r i c i a l r u l e , t h e l o w e s t o r b i t f o r an o u t e r
e l e c t r o n in a n e u t r a l a t o m is t h e one f o r which (a) the s u m of p r i n c i p a l
and o r b i t a l quantum n u m b e r s , n + Í , h a s t h e l o w e s t value and which (b) f o r e q u a l
v a l u e s of (n + i ) h a s the l o w e s t n. T h i s would l e a d to t h e following o r d e r
of o r b i t s in n e u t r a l a t o m s : I s , 2s, 2p, 3s, 3p, 4 s , 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, . . .
which so f a r a g r e e s with o b s e r v a t i o n s , except t h a t one 5 d - e l e c t r o n is bound
b e f o r e the f i r s t 4 f - e l e c t r o n . With i n c r e a s i n g s t a g e of ionization, h o w e v e r ,
it f o l l o w s f r o m e l e m e n t a r y a r g u m e n t s that t h e s y s t e m will a p p r o a c h t h e
h y d r o g e n - l i k e c a s e in which t h e binding e n e r g y is d e t e r m i n e d by the v a l u e
of n and f o r e q u a l n by Í , T h u s , a f t e r the 4 d - s h e l l h a s been filled at
N = 46, then 4f i s t h e o r b i t t h a t f o r high enough e f f e c t i v e c h a r g e Ç should
b e c o m e t h e m o s t tightly bound. H o w e v e r , b e f o r e that o c c u r s , the l o w e s t
p o s i t i o n will be occupied by a v a r i e t y of o t h e r o r b i t s , n a m e l y 5 s , 5p, 6s
and 5d, l e a d i n g to a s e r i e s of d r a s t i c g r o u n d - c o n f i g u r a t i o n t r a n s f o r m a t i o n s
as one goes up t h r o u g h t h e s e q u e n c e s (see T a b l e XI).
While 5s can be e x p e c t e d to hold i t s p o s i t i o n quite f a r up, t h e o r b i t 5p
will r e l a t i v e l y soon be m a t c h e d by 4f. At t h a t s t a g e a s m a l l i n c r e a s e in
128 EDLEN
FIG.30. T h e c o n f i g u r a t i o n s 3 d 2 , 3d4s and 4s z in t h e Ca I i s o e l e c t r o n i c s e q u e n c e .
e f f e c t i v e c h a r g e Ç will be s u f f i c i e n t f o r having t h e 5 p - o r b i t s all at once

r e p l a c e d by 4f [6]. In t h e Xe s e q u e n c e , f o r i n s t a n c e , t h e c o l l a p s e of the
5p s h e l l will c a u s e the s i n g l e ground l e v e l 5pS to be r e p l a c e d by t h e
h u n d r e d s of l e v e l s of 4 f 6 . T h i s d r a m a t i c event h a s b e e n o b s e r v e d by R e a d e r
and E k b e r g (unpublished). T h e y found t h e five r e s o n a n c e t r a n s i t i o n s in t h e
X e I - l i k e s p e c t r a a s o u t s t a n d i n g and e a s i l y i d e n t i f i e d l i n e s up to Ce V.
In P r VI s o m e of t h e l i n e s could still be r e c o g n i z e d , w h e r e a s t h e s p e c t r u m
of Nd had the a p p e a r a n c e of a continuum f o r m e d by i n n u m e r a b l e faint l i n e s .
A t e r m a n a l y s i s of t h i s s p e c t r u m is, of c o u r s e , i m p o s s i b l e . T h u s , f r o m
t h e p r a c t i c a l point of view, t h e Xe s e q u e n c e t e r m i n a t e s with P r VI.
In t h e following s e q u e n c e s (group Via in T a b l e XI) we find s i m i l a r
t r a n s f o r m a t i o n s with i n c r e a s i n g c o m p l e x i t y , until f o r N = 68 t h e a s y m p t o t i c
ground c o n f i g u r a t i o n h a s again r e a c h e d t h e s i m p l e c a s e of f i l l e d s h e l l s .
lAEA-SMR-12/4, 5 129
FIG.31. T h e configurations 3 d " , 3d 9 4s a n d 3 d 8 4 s 2 in t h e Ni I i s o e l e c t r o n i c s e q u e n c e .

130 EDLEN
T A B L E XI. GROUND CONFIGURATIONS FOR ATOMS AND IONS IN T H E

SECOND H A L F O F T H E PERIODIC SYSTEM
a
Period N Configuration Spectrum
С 47 5s (-> 4 f ) A g i , C d l l , InlII
Vb -j 48 5s 2 (-> 4 P ) Cdl, Inll, Snin,...

2 k 2 k k+
L 49-54 5s 5 p - > 5s 4 f (-> 4 f 2) I n ( l ) , Sn(2), Sb(3), T e ( 4 ) , 1(5), Xe(6)
55 5s 2 5 p 6 6 s - » 5s z 5рБ 5d-> 5 s 2 5 p « 4 f - > 5 s 2 4 f ( - 4 f 9 ) Csl,...

2 6 2 z 6 2 2 8 10
56 5s 5p 6s . . . -- 5s 5p 4 f 5s 4f (-> 4 f ) Bal,...
57 5s 2 5p 6 6s 2 Sd ->• . . . - 5s 2 5p6 4f 3-> 5 s 2 4 f s ( - 4 f " ) Lai, . . .
' Via
60 5s 2 5p 6 6s 2 4f4-> . . . - > 5s 2 5 p 6 4 f 6 - * 5 s 2 4 f l 2 ( ^ 4 f i 4 ) Ndl
62 5s 2 5 p 6 6 s 2 4 f 6 - » . . .-> 5 s 2 5 p 6 4 f s - » 5 s 2 4 f " SmI,...
68 5s 2 5p 6 6 s 2 4 f 1 2 - » . . . 5s 2 5p 6 4 f 1 4 Erl, . . .
Г 69 6s z 4 f i 3 - > . . .-> 4 f « 5 d T m i , У b u , LuIII
VIb i 70 6s z 4f 14 -> . . .-> 4Í 1 4 5d 2 Y b l , Lull, H f l l I , .. .
L 71-78 6s 2 5 d k - 2 -*• 5 d k Lu(3), Н Й 4 ) , T a ( 5 ) , W(6), Re(7), Os(8),

Ir(9), Pt(10)
Г 79 6s ( - 5f) A u l , HglI, T1III
Vic j 80 6s 2
(-» 5 f ) 2
H g l , T l i l , РЫН
L 81-86 6s 2 6 p k - 6s 2 5 f ! < ( - 5 f k + 2
) T l ( l ) , Pb(2), Bi(3), Po(4), A t ( 5 ) , Rn(6)
VII 87... similar to 5 5 . . .
a
In t h e first s p e c t r a of t h e l a n t h a n i d e s t h e ground s t a t e is p r o v i d e d by 6s 2 5d4f k for
Z(= N) = 5 7 , 58, 6 4 a n d by 6 s 2 4 f k + 1 in a l l o t h e r c a s e s [ 2 ] .
\
In t h e g r o u p c a l l e d VIb in T a b l e XI, c o m p r i s i n g the 10 s e q u e n c e s N = 69 - 7 8,

the g r o u n d c o n f i g u r a t i o n s a r e quite a n a l o g o u s to t h o s e in t h e p r e v i o u s two
g r o u p s of t r a n s i t i o n e l e m e n t s , except f o r t h e m o d i f i c a t i o n c a u s e d by one hole
in t h e 4 f - s h e l l in t h e v e r y beginning of s e q u e n c e 69. We note, f i n a l l y , t h a t
the e l e c t r o n i c s y s t e m s s t a r t i n g f r o m N = 79 will be c l o s e l y s i m i l a r to t h o s e
s t a r t i n g f r o m N = 47.
This s k e t c h of t h e e l e c t r o n i c s t r u c t u r e of t h e i s o e l e c t r o n i c s e q u e n c e s
t h r o u g h t h e P e r i o d i c T a b l e h a s been m a i n l y c o n c e r n e d with t h e ground
c o n f i g u r a t i o n s , which to a c o n s i d e r a b l e extent d e t e r m i n e t h e g e n e r a l
c h a r a c t e r of a s p e c t r u m . H o w e v e r , a d d i t i o n a l c o m p l e x i t i e s a r e i n t r o d u c e d
in t h e t e r m s y s t e m s by t h e e x c i t a t i o n of i n n e r s h e l l s , a s f o r i n s t a n c e
e x c i t a t i o n of 3 s 2 3 p 6 3 d k to 3 s 2 3 p 5 3 d k + 1 , f o r which the p o s s i b i l i t i e s tend to
i n c r e a s e with i n c r e a s i n g N.
IAEA-SMR-12/4, 5 131
4. 3. B r i e f s u r v e y of l i t e r a t u r e on t e r m a n a l y s i s
The r e s u l t s of the g r e a t n u m b e r of a n a l y s e s m a d e s i n c e the p u b l i c a t i o n

of C h a r l o t t e E. M o o r e ' s " A t o m i c E n e r g y L e v e l s " [8] m u s t f o r the m o s t p a r t
be r e t r i e v e d f r o m o r i g i n a l p a p e r s s c a t t e r e d in v a r i o u s p u b l i c a t i o n s . New
v e r s i o n s of t h e A E L T a b l e s a r e a s y e t a v a i l a b l e only f o r С I-VI, N IV-VII
and Si I - I V [10]. As a r e m e d y to t h i s d i f f i c u l t y c o m p r e h e n s i v e c o l l e c t i o n s
of r e f e r e n c e s to a n a l y s e s of a t o m i c s p e c t r a h a v e b e e n p r o d u c e d at t h e
US N a t i o n a l B u r e a u of S t a n d a r d s , one c o v e r i n g the l i t e r a t u r e up to 1968-69
[9] and a s e c o n d one continuing t h r o u g h J u n e 1971 [7]. A f u r t h e r c o n t r i -
bution to t h i s end m a y be found in Ref. [5] which g i v e s a l i s t of p a p e r s that
s u p p l e m e n t the i n f o r m a t i o n contained in A E L . In c o n t r a s t to t h e b i b l i o -
g r a p h i e s m e n t i o n e d above, t h i s c o m p i l a t i o n is c r i t i c a l and s e l e c t i v e in the
s e n s e that in p r i n c i p l e only t h o s e p a p e r s a r e l i s t e d which we find n e c e s s a r y
to c o n s u l t in o r d e r to obtain all i n f o r m a t i o n now a v a i l a b l e on t h e e n e r g y
l e v e l s y s t e m s of t h e s p e c t r a c o n c e r n e d . The c o m p i l a t i o n i s l i m i t e d to
Z s 28, and a s o m e w h a t a r b i t r a r y l i m i t h a s been s e t to t h e d e g r e e of
ionization. It i s c a r r i e d t h r o u g h N o v e m b e r 1972 and r e p r e s e n t s an
e n l a r g e d v e r s i o n of an e a r l i e r a t t e m p t [3] to p r o v i d e a convenient key to
the l i t e r a t u r e .
REFERENCES
[1] ACCAD, Y . , PEKERIS, C . L . , SCHIFF, В . . Phys. Rev. A 4 (1971) 516.

[2] BREWER, L . , J. O p t . Soc. A m . 61 (1971) 1101.
[3] EDLEN, В . , N u c l . Instrum. Methods, 90 (1970) 1.
[4] EDLEN, В . , O p t i c a Рига y A p l i c a d a 5 (1972) 101.
[5] EDLEN, В . , Physica Scripta 7 (1973) 93.
[6] GRIFFIN, D . C . , ANDREW, K . C . , COWAN, R . D . , Phys. Rev. П 7 (1969) 62.
[7] HAGAN, L . , MARTIN, W . C . , Bibliography o n A t o m i c Energy Levels and Spectra, N a t . Bur. S t a n d .
( U . S . ) , S p e c i a l P u b l . 363 (1972).
[8] MOORE, C . E . , A t o m i c Energy Levels, N a t . Bur. Stand. ( U . S . ) Circular 467, V o l . 1 (1949), V o l . 2 (1952),
V o l . 3 (1958).
[9] MOORE, C . E . , Bibliography of t h e Analyses of O p t i c a l A t o m i c S p e c t r a , N a t . Bur. S t a n d . ( U . S . ) ,
S p e c i a l P u b l . 306, S e c t . 1 (1968), S e c t . 2 , 3 , 4 (1969).
[10] MOQRE, C . E . , S e l e c t e d T a b l e s of A t o m i c S p e c t r a , N a t . S t a n d . Ref. Data Series. Nat. Bur. S t a n d . ( U . S . ) ,
3, Sect 1 - 4 ( 1 9 6 5 - 1 9 7 1 ) .
[11] EDLEN, В . , " A t o m i c s p e c t r a " , H a n d b . der Physik 27, Springer, Berlin (1964),
[12] EDLEN, В . , " I o n i z a t i o n p o t e n t i a l s of a t o m s and ions c o n t a i n i n g o n e to 10 e l e c t r o n s " ,
Modern Physics (BRITTIN, W . E . , ODABASI, H . , Eds), Colorado Univ. Press, Boulder (1971).
[13] EDLEN, В . , Phys. Rev. Lett. 28 (1972) 943.
[14] EDLEN, В . , Solar Physics 9 (1969) 4 3 9 .
[15] EDLEN, В . , Solar Physics 24 (1972) 356.
[16] SVENSSON, L . A . , Solar Physics 18 (1971) 232.
IAEA-SMR-12/12
LINE WIDTH AND LINE BROADENING
W.R. HINDMARSHT
Department of Atomic Physics,
University of Newcastle-upon-Tyne,
United Kingdom
Abstract
LINE WIDTH A N D LINE BROADENING.

Collision broadening, classical theory; quasi-static approximation; q u a n t u m t h e o r y of c o l l i s i o n
broadening; i n v e r s e p o w e r and L e n n a r d - J o n e s p o t e n t i a l s , i m p a c t a p p r o x i m a t i o n , quasi-static approximation,
g e n e r a l t h e o r y , r e s u l t s of m e a s u r e m e n t s , c o m p a r i s o n b e t w e e n t h e o r y and e x p e r i m e n t ; b r o a d e n i n g by c h a r g e d
p a r t i c l e s , q u a d r a t i c S t a r k e f f e c t , i n f l u e n c e of i n e l a s t i c collisions; b r o a d e n i n g t h r o u g h l i n e a r Stark e f f e c t .
1. CLASSICAL THEORY O F COLLISION BROADENING
1.1. General formulation
T h e c l a s s i c a l m o d e l t r e a t s an a t o m i c r a d i a t o r a s an e l a s t i c a l l y bound
o s c i l l a t i n g e l e c t r o n . T h e p r o b l e m of c o l l i s i o n b r o a d e n i n g i s to c a l c u l a t e
the s p e c t r u m of s u c h an o s c i l l a t o r w h e n it is d i s t u r b e d by c o l l i s i o n s with
the o t h e r a t o m s in i t s e n v i r o n m e n t . We a s s u m e t h a t the c o l l i s i o n s do not
change t h e a m p l i t u d e of the o s c i l l a t o r , but only t h e p h a s e . T h i s i s e q u i v a l e n t
to a s s u m i n g t h a t t h e t r a n s i t i o n p r o b a b i l i t y i s unchanged by the c o l l i s i o n .
The d i s p l a c e m e n t of the o s c i l l a t o r a s a f u n c t i o n of t i m e i s given by
t > 0 (1)
о
w h e r e u ' ( t ' ) i s t h e i n s t a n t a n e o u s a n g u l a r f r e q u e n c y of the o s c i l l a t i o n at

t i m e ť and Re s t a n d s f o r " r e a l p a r t o f " . T h e u n d i s t u r b e d f r e q u e n c y will
be r e p r e s e n t e d by u 0 , and the o s c i l l a t i o n b e g i n s a t t = 0. The e f f e c t of
n a t u r a l d a m p i n g is i g n o r e d . It i s , in f a c t , o f t e n n e g l i g i b l e c o m p a r e d with
c o l l i s i o n a l e f f e c t s , but in t h e i m p a c t a p p r o x i m a t i o n t h e e f f e c t s of n a t u r a l and
c o l l i s i o n a l d a m p i n g a r e a d d i t i v e . T h e i n t e n s i t y p r o f i l e I(u) of the light
e m i t t e d by t h e o s c i l l a t o r i s t h e n given by
(2)
^ I t is w i t h r e g r e t t h a t t h e p u b l i s h e r r e c o r d s t h e d e a t h of Professor H i n d m a r s h i n D e c e m b e r 1 9 7 3 .
133
134 HIND MARSH
An e q u i v a l e n t g e n e r a l e x p r e s s i o n is found by using the a u t o c o r r e l a t i o n

f u n c t i o n of t h e d i s t u r b a n c e f(t). P u t t i n g
J d t ' u ' ( t ' ) = u 0 t + 17(t)

0
w h e r e 17(t) i s t h e d e p a r t u r e in p h a s e of the p e r t u r b e d o s c i l l a t i o n f r o m t h e
u n p e r t u r b e d o s c i l l a t i o n , t h e a u t o c o r r e l a t i o n f u n c t i o n Ф(в) i s
2
Ф(в) = f(t) f(t + s) = I e i ^ 0 t e i w 0 s e i [ T i ( t + s) + j j ( t ) ]
t
+ R e Í . 'i w o S „ i [ l ) ( t + s ) - 7j(t)]
J
w h e r e I It i n d i c a t e s the a v e r a g e value o v e r a l l v a l u e s of t . The f i r s t t e r m

in t h e e x p r e s s i o n f o r ®(s) v a n i s h e s p r o v i d e d t h a t no s i g n i f i c a n t d i s t u r b a n c e
in p h a s e o c c u r s , on t h e a v e r a g e , within one c y c l e of o s c i l l a t i o n . F o r o p t i c a l
s p e c t r a , w h e r e t h e line width i s a s m a l l f r a c t i o n of t h e u n d i s t u r b e d f r e q u e n c y ,
t h i s i s a v e r y good a p p r o x i m a t i o n , but it should be noticed t h a t t h e r e s u l t s
obtained with i t s u s e c a n n o t be e x t r a p o l a t e d to give t h e c o r r e c t z e r o -
f r e q u e n c y r e s u l t s . With t h i s l i m i t a t i o n we m a y w r i t e
Ф(в) = -H Re giwos gii(t.s)
+ e- i w 0 s g-itKM)
(3)
= Ф(в) + \ř*(s)
w h e r e n(t, s) = n(t + s) - r)(t).

Since the i n t e n s i t y p r o f i l e i s the c o m p l e x F o u r i e r t r a n s f o r m of the a u t o -
c o r r e l a t i o n f u n c t i o n of the d i s t u r b a n c e we have
I (to) = M / ( s ) e l a J S ds + / Ф* (s)e l w s ds (4)
1.2. The i m p a c t a p p r o x i m a t i o n
T h e c h a n g e Д [^(sje" 1 " 0 5 ], not n e c e s s a r i l y s m a l l , in Sř(s)e"1WoS c o r r e -

sponding to a c h a n g e A s in s i s
A[*(s)e-iw°s] (e i A l i - l ) ] t
i , M
=|le l t [e iAl) - 1],
= -ф(в)е - i w 0 s r i At)
- Ht
where Arj = r)(t, s + A s ) - r)(t, s)

IAEA-SMR-12/4,5 135
and the s e c o n d line f o l l o w s b e c a u s e the c h a n g e s Ar] o c c u r r i n g in an o s c i l -

l a t o r p e r t u r b e d by r a n d o m c o l l i s i o n s a r e s t a t i s t i c a l l y i n d e p e n d e n t of rj,
the a c c u m u l a t e d p h a s e d i s t u r b a n c e a t t i m e s . Next we s u p p o s e t h a t t h e
p h a s e c h a n g e s Дт] a r e c a u s e d by s u c c e s s i v e c o l l i s i o n s . T h i s i s known a s
t h e i m p a c t a p p r o x i m a t i o n , and we s h a l l d i s c u s s i t s r a n g e of v a l i d i t y l a t e r .
T h e n u m b e r of c o l l i s i o n s with i m p a c t p a r a m e t e r p which o c c u r in t h e t i m e
i n t e r v a l A s i s NV2îrp dp | A s | w h e r e N i s t h e n u m b e r d e n s i t y of p e r t u r b i n g
p a r t i c l e s ; t h e f u r t h e r a s s u m p t i o n h a s b e e n m a d e t h a t the p e r t u r b i n g and
r a d i a t i n g a t o m s m o v e in s t r a i g h t l i n e s with t h e m e a n r e l a t i v e v e l o c i t y v .
Then
[eiAr> - l ] t = 2 7 r N v | A s | / [ e i , K p ) - 1] pdp
о
= - N v I A s I (ст - iCTj )
w h e r e rj(p) i s t h e p h a s e c h a n g e c a u s e d by a c o l l i s i o n of i m p a c t p a r a m e t e r p,
and
crr = 2 n J [ 1 - c o s rj(p)] pdp (5)

о
CTj = 2nJ s i n rj (p) pdp (6)

о
Therefore
L = - Nv I A s I (стг - iCTj )
*(s)e~ l a , » s
Since the a v e r a g e o v e r a l a r g e n u m b e r of c o l l i s i o n s i s i n v o l v e d , t h i s l a s t
e x p r e s s i o n c a n be t r e a t e d a s a d i f f e r e n t i a l e q u a t i o n . I n t e g r a t i o n t h e n g i v e s
Ф(э) = c o n s t a n t X exp Uiw 0 - N v ( a r - iOj ) ] | s | } (7)
T h u s the s p e c t r u m i s , f r o m E q s (4) and (7),
I(u>) = 2NVa r { ( u ) o + u + Ша.уг + {Ша!уг + ( Uo . ш + Ш а ^ + (NVtrr ) и } (8)
In o p t i c a l s p e c t r a t h e f i r s t t e r m i n t h i s e x p r e s s i o n f o r I(u) i s n e g l i g i b l e •
c o m p a r e d with the s e c o n d . T h u s
(u0 - ы + Nva ř )2 + (Nvar )2
w h e r e we have n o r m a l i z e d so t h a t
ОС
f I(u)du = 1
о
136 HIND MARSH
T h e s p e c t r a l line t h e r e f o r e h a s a L o r e n t z i a n s h a p e , but the whole line

i s s h i f t e d with r e s p e c t to t h e u n d i s t u r b e d line c e n t r e at u 0 . The quantity
a r - i n j c a n b e looked on a s a c o m p l e x c r o s s - s e c t i o n , t h e b r o a d e n i n g of
the line being a s s o c i a t e d with the r e a l p a r t of t h i s c r o s s - s e c t i o n and
t h e s h i f t with t h e i m a g i n a r y p a r t -ст ; . It i s a l s o e a s y to s e e f r o m E q s (5)
and (6) t h a t , s i n c e n(p) i n c r e a s e s r a p i d l y a s p d e c r e a s e s , t h e c o n t r i b u t i o n
to CTj a r i s e s p r e d o m i n a n t l y f r o m s m a l l v a l u e s of p while t h a t to a r a r i s e s
p r e d o m i n a n t l y f r o m l a r g e v a l u e s of p. T h i s c o r r e s p o n d s to the o r i g i n a l
p h y s i c a l i d e a of W e i s s k o p f (1933) that t h e b r o a d e n i n g a r i s e s e s s e n t i a l l y
f o r c o l l i s i o n s which c a u s e a p h a s e c h a n g e g r e a t e r t h a n about 1 r a d i a n .
To p r e s s t h i s c l a s s i c a l c a l c u l a t i o n to a n u m e r i c a l c o n c l u s i o n we m u s t
e v a l u a t e n(p) and p e r f o r m t h e i n t e g r a t i o n s in E q s (5) and (6). If t h e i n t e r -
a t o m i c p o t e n t i a l s of the u p p e r and l o w e r s t a t e s of the r a d i a t i n g a t o m and
the p e r t u r b i n g a t o m (taken to be in t h e g r o u n d s t a t e ) a r e r e s p e c t i v e l y Vu (R)
and V j i R ) , w h e r e R i s t h e d i s t a n c e b e t w e e n t h e two a t o m s , then
SO OO
4(p) = ^ / [ V u ( R ) - V , ( R ) ] d t V(R)dt
w h e r e t r e p r e s e n t s the t i m e m e a s u r e d f r o m t h e t i m e of c l o s e s t a p p r o a c h
of t h e colliding a t o m s . If we a s s u m e t h a t the a t o m s m o v e i n s t r a i g h t p a t h s
with v e l o c i t y v, then,
„2 2 2 2
R =p + v t
so that
2 Г V(R) RdR
«M - WJ (R2 - p ž )i (10)
о
We now e x a m i n e the v a l i d i t y of the i m p o r t a n t a p p r o x i m a t i o n s which have

been made.
F i r s t we c o n s i d e r t h e i m p a c t a p p r o x i m a t i o n i t s e l f . T h e c o l l i s i o n s a r e
s u p p o s e d to o c c u r s u c c e s s i v e l y and to occupy a t i m e s m a l l c o m p a r e d with
t h e t i m e b e t w e e n c o l l i s i o n s . The r a d i a t i o n e m i t t e d d u r i n g the c o l l i s i o n s
m a y then be n e g l e c t e d . Now t h e d u r a t i o n of a c o l l i s i o n i s т с ~ p / v and the
m e a n t i m e b e t w e e n c o l l i s i o n s which c a u s e b r o a d e n i n g i s 7 = (Nvo r ) _1 . We
c o m p a r e the i n t e n s i t y p e r unit f r e q u e n c y i n t e r v a l f r o m т с with t h a t f r o m т
a t a given f r e q u e n c y d i s p l a c e m e n t (uQ - u) f r o m the l i n e c e n t r e . R e m e m b e r i n g
t h a t the f o r m e r c o n t r i b u t i o n i s s p r e a d o v e r an i n t e r v a l ~ т" 1 , the r a t i o of the
two c o n t r i b u t i o n s i s a p p r o x i m a t e l y
2 2 2 2
(p/v) 7Г (U)Q - U) _ 7Tp (Up -(O)
(Nva r )-l NvCTr V2
If the i m p a c t a p p r o x i m a t i o n i s to be v a l i d t h i s r a t i o m u s t be « 1. Hence
(u 0 - u) 2 « V 2 / t t P 2 (11)
IAEA-SMR-12/4,5 137
But t h e v a l u e of u 0 - u a s s o c i a t e d with a c e r t a i n v a l u e of p i s d e t e r m i n e d
by the i n t e r a t o m i c p o t e n t i a l
u 0 - u = - V(p)/tl
6
In the s p e c i a l c a s e of the v a n - d e r - W a a l s i n t e r a c t i o n s V(p) = - Cg/R , the
inequality b e c o m e s
6/5 1/5
(12)
F o r n e u t r a l a t o m p a i r s C 6 ~ 10 5 1 e r g • cm 6 , and f o r m a n y e x p e r i m e n t s
v = 10 5 c m • s" 1 . With t h e s e v a l u e s , we find the i m p a c t r e g i o n d e f i n e d a s
I со q - и I « 3X 1 0 U r a d - s " 1 = 1,5 cm" 1
Although v a l u e s of C g and v c a n v a r y o v e r a c e r t a i n r a n g e , the i m p a c t r e g i o n

i s m o s t l y d e f i n e d by a b o u n d a r y of a few wave n u m b e r s . Notice t h a t t h i s
b o u n d a r y o c c u r s on one wing only of t h e line if the p o t e n t i a l i s e n t i r e l y
d e s c r i b e d by the v a n - d e r - W a a l s i n t e r a c t i o n . If C 6 i s p o s i t i v e (the u s u a l
c a s e ) , t h e n u 0 - ш i s p o s i t i v e and the b o u n d a r y r e f e r s to t h e low f r e q u e n c y
wing of t h e l i n e , and the i m p a c t a p p r o x i m a t i o n i s v a l i d f o r all p o s i t i o n s
on the high f r e q u e n c y wing of the l i n e . In f a c t , f o r v e r y c l o s e e n c o u n t e r s
the " r e p u l s i v e " p a r t of t h e p o t e n t i a l c u r v e c a u s e s r a d i a t i o n to be e m i t t e d
on the high f r e q u e n c y side of t h e line c e n t r e , so t h a t in p r a c t i c e an i m p a c t
b o u n d a r y a r i s e s on that side a l s o . Taking t h e L e n n a r d - J o n e s f o r m
V(p) = C 1 2 / p 1 2 - C 6 / p 6 i t t u r n s out, with t y p i c a l v a l u e s f o r the c o n s t a n t s ,
t h a t t h e i m p a c t b o u n d a r y on t h e l o w - f r e q u e n c y side i s not usually a f f e c t e d
by the p r e s e n c e of the R" 12 t e r m , and that on t h e h i g h - f r e q u e n c y s i d e the
b o u n d a r y i s d e t e r m i n e d only by t h e r e p u l s i v e t e r m . With C 12 = 10" 1 0 4 e r g - c m 1 2
and v = 10 5 c m - s 1 , we find
|u 0 - u | « 3 X 1 0 1 2 r a d - s " 1 = 15 cm" 1
A n o t h e r s p e c i a l c a s e of s o m e i m p o r t a n c e i s t h e i n t e r a c t i o n of c h a r g e d
p a r t i c l e s with a n e u t r a l a t o m . In g e n e r a l t h i s t a k e s the f o r m of a q u a d r a t i c
S t a r k e f f e c t and i s t h e r e f o r e d e s c r i b e d by the e x p r e s s i o n C 4 / R 4 . T h e
i m p a c t r e g i o n i s then d e f i n e d by the r e l a t i o n
/ \4/3 , .1/3
к @
V a l u e s of C 4 g e n e r a l l y lie in t h e r a n g e 10"39 -10" 4 2 e r g • c m 4 . We need
to d i s t i n g u i s h t h e b r o a d e n i n g due to ions, with t h e r m a l v e l o c i t i e s of s a y
2X10 cm • s in a low t e m p e r a t u r e p l a s m a , and t h a t due to t h e e l e c t r o n s
with v e l o c i t i e s of p e r h a p s 5 X 10 7 c m • s" 1 . F o r ion b r o a d e n i n g we find
u 0 - u | « 5X 10 10 - 5 X 1 0 1 1 r a d - s " 1 = 0 . 3 - 3 cm" 1
138 HIND MARSH
while f o r e l e c t r o n b r o a d e n i n g t h e r e s u l t i s
I Up - u | « 10 1 4 - 10 15 r a d • s 1
= 500 - 5000 cm" 1
F i n a l l y we e x a m i n e t h e r a n g e of v a l i d i t y of t h e i m p a c t a p p r o x i m a t i o n
when h y d r o g e n - l i k e l i n e s a r e b r o a d e n e d by e l e c t r o n s and i o n s . H e r e the
l i n e a r S t a r k e f f e c t g o v e r n s the i n t e r a c t i o n which t a k e s the f o r m C 2 / R 2 ,
and we find
F o r a h y d r o g e n a t o m C 2 ~ e 2 a 0 n ( n - l ) w h e r e n i s the p r i n c i p a l q u a n t u m
n u m b e r of t h e u p p e r l e v e l . F o r H a C , = 5X 10" 27 e r g - c m 2 . With
~ - 2 X 10 5 c m • s" 1 f o r i o n s and 5 X 10* c m • s" 1 f o r e l e c t r o n s we find
9
|Uq - u I <c 10 r a d • s" 1 = 0.005 cm" 1
f o r the i m p a c t l i m i t f o r ionic b r o a d e n i n g and
ш„ - w « 10 1 4 r a d • s" 1 = 500 cm" 1
f o r ionic b r o a d e n i n g .
Secondly we e x a m i n e the v a l i d i t y of the a s s u m p t i o n t h a t the a t o m s m o v e
in s t r a i g h t l i n e s . A r o u g h c a l c u l a t i o n c a n be m a d e to e s t i m a t e the r a n g e of
a p p l i c a b i l i t y of the s t r a i g h t - p a t h a p p r o x i m a t i o n .
T h e o r b i t will be s i g n i f i c a n t l y c u r v e d if the i m p u l s e of the f o r c e F
e x e r t e d b e t w e e n t h e colliding a t o m s b e c o m e s c o m p a r a b l e with the m o m e n t u m
of e i t h e r of t h e m . T h e r e l e v a n t r a t i o i s t h e r e f o r e , f o r n e u t r a l a t o m s ,
/Fdt ^ (dV/dR) R , g p _ S 2 Ci2 Ce

P
Mv Mv v Mv 2 n i2 " «6
w h e r e M i s the m a s s of the s m a l l e r a t o m involved. Now t h e p h a s e c h a n g e ,

calculated for straight paths, for a L e n n a r d - J o n e s potential is (Hindmarsh,
P e t f o r d and Smith, 1967)
63£ Olg 3_7T J _ Cg
1 K
256 m p H " 8 TiV p5 '
If, at the c r i t i c a l v a l u e p c of p, r) is d e t e r m i n e d e s s e n t i a l l y by the s e c o n d

t e r m , t h e n p i s a l s o so d e t e r m i n e d . We t h e n h a v e , s i n c e rj = 1 at p c ,
P® ~ c . / w
6
and
6tt 6tl6/5
Л
MVpc Mv4/5Cl/5 "" °
IAEA-SMR-12/4,5 139
on s u b s t i t u t i n g t y p i c a l v a l u e s . P a t h c u r v a t u r e i s t h e r e f o r e s m a l l . If C 6
i s s m a l l , p c i s e s s e n t i a l l y d e t e r m i n e d by the R" 12 t e r m . In t h i s c a s e we
find p ~ 1 with C 1 2 = 10" 106 e r g - c m 1 2 . We t h e r e f o r e e x p e c t p a t h c u r v a t u r e
to have a m a r k e d e f f e c t .
F o r c h a r g e d - p a r t i c l e i n t e r a c t i o n s we find f o r the q u a d r a t i c S t a r k e f f e c t
interaction
10
P ~ Mv2/3 c i / 5 ~ "3 - 10 2
" for ions
% 0.3 - 3.0 for electrons
and f o r t h e l i n e a r S t a r k e f f e c t i n t e r a c t i o n
2ft 2 1 n -4 , .
10 for ions
MC 2
1 for electrons
We t h e r e f o r e e x p e c t t h a t c u r v a t u r e of the o r b i t s i s i m p o r t a n t f o r i m p a c t
b r o a d e n i n g by e l e c t r o n s but not f o r b r o a d e n i n g by i o n s . A f u n d a m e n t a l
point which a r i s e s h e r e i s how to c o m b i n e t h e p o t e n t i a l s f o r the two l e v e l s
of the r a d i a t o r which a r e involved in the t r a n s i t i o n , s i n c e the c l a s s i c a l
p a t h will not be the s a m e f o r both l e v e l s . T h i s h a s b e e n d i s c u s s e d by
F i u t a k and C z u c h a j (1970) who point out t h a t the condition p « 1 f o r s t r a i g h t
p a t h s i s e s s e n t i a l l y t h e s a m e a s the condition f o r t h e p e r t u r b e r m o t i o n to
be d e s c r i b e d c l a s s i c a l l y at all (see s e c t i o n 2). Although S c h ü l l e r and V o d a r
(1960) have c a l c u l a t e d t h e e f f e c t of c u r v a t u r e of the o r b i t s f o r a S u t h e r l a n d
t y p e of p o t e n t i a l , and find s i g n i f i c a n t e f f e c t s in c e r t a i n c r i c u m s t a n c e s , a
g r e a t e r e f f o r t i s p r o b a b l y not w o r t h while u n l e s s a f u l l q u a n t u m m e c h a n i c a l
treatment is used.
T h i r d l y we m e n t i o n the p r o b l e m of v e l o c i t y a v e r a g i n g . In m o s t w o r k
t h i s i s a c h i e v e d by t h e s i m p l e d e v i c e of w r i t i n g v , the m e a n t h e r m a l r e l a t i v e
s p e e d of t h e r a d i a t i n g and p e r t u r b i n g a t o m s w h e r e v e r t h e v e l o c i t y e n t e r s
the c a l c u l a t i o n . ,This i s c l e a r l y not c o r r e c t . It i s a r e l a t i v e l y s i m p l e m a t t e r
to a v e r a g e the p h a s e s h i f t e x p r e s s i o n s o v e r a M a x w e l l i a n v e l o c i t y d i s t r i b u t i o n ,
and t h i s in f a c t m a k e s only a s m a l l d i f f e r e n c e to the n u m e r i c a l r e s u l t s . The
r e a l d i f f i c u l t y i s t h a t if r i g o r o u s l y c o r r e c t v e l o c i t y a v e r a g i n g i s to be c a r r i e d
out, the t h e r m a l (Doppler) b r o a d e n i n g of t h e s p e c t r a l line cannot be t r e a t e d
s e p a r a t e l y f r o m the c o l l i s i o n b r o a d e n i n g a s i s u s u a l l y done. T h i s q u e s t i o n
h a s b e e n s t u d i e d by G e r s t o n and F o l e y (1968). who r e f e r to the e a r l i e r w o r k
of Dicke (1953) and W i t t k e and Dicke (1956) on " p r e s s u r e n a r r o w i n g " . The
e s s e n t i a l point i s t h a t if the m e a n f r e e path of t h e r a d i a t i n g a t o m s f o r c o l -
l i s i o n s w h i c h change t h e i r d i r e c t i o n b e c o m e s m u c h s m a l l e r t h a n t h e w a v e l e n g t h
of t h e r a d i a t i o n , t h e D o p p l e r s h i f t induced in one p o r t i o n of a c y c l e of the
r a d i a t i o n t e n d s to c a n c e l t h e s h i f t f r o m a n o t h e r p o r t i o n . The e f f e c t i v e
D o p p l e r width i s t h e n m u c h r e d u c e d , and p r o v i d e d the o r d i n a r y c o l l i s i o n
b r o a d e n i n g i s not too g r e a t , a n e t n a r r o w i n g with i n c r e a s i n g p r e s s u r e c a n
o c c u r o v e r a c e r t a i n p r e s s u r e r a n g e . T h i s i s not u s u a l l y the c a s e in o p t i c a l
s p e c t r a , but at m u c h l o w e r f r e q u e n c i e s t h e p h e n o m e n o n i s w e l l known.
140 H I N D MARSH
1.3. The quasi-static approximation
The q u a s i - s t a t i c approximation t a k e s into account r a d i a t i o n emitted

a t a l l t i m e s , but d o e s not m a k e a F o u r i e r a n a l y s i s . T h e i n t e n s i t y a t an
a n g u l a r f r e q u e n c y u i s t h u s p r o p o r t i o n a l to t h e f r a c t i o n of t h e t o t a l t i m e
w h i c h the a t o m s p e n d s i n r a d i a t i n g at t h a t f r e q u e n c y . If t h e i n s t a n t a n e o u s
f r e q u e n c y i s r e p r e s e n t e d by u - L)q + Au t h e n t h e q u a s i - s t a t i c t h e o r y g i v e s
I (Ди) ос P ( A u )
w h e r e Р(Аы) i s t h e p r o b a b i l i t y of o c c u r r e n c e of t h e f r e q u e n c y d i s p l a c e m e n t
Au.
We w i s h to e v a l u a t e t h e o c c u r r e n c e p r o b a b i l i t y P ( A u ) in t e r m s of t h e
i n t e r a t o m i c p o t e n t i a l . T h i s t y p e of c a l c u l a t i o n w a s f i r s t p e r f o r m e d by
H o l t s m a r k (1919) f o r the s p e c i a l c a s e of b r o a d e n i n g by c h a r g e d p a r t i c l e s
(where the i n t e r a c t i o n is e i t h e r the linear or the quadratic Stark effect)
and by M a r g e n a u (1932) f o r the g e n e r a l c a s e of s c a l a r l y a d d i t i v e i n t e r a c t i o n s .
We show h e r e t h e c a l c u l a t i o n s f o r the l a t t e r c a s e .
I m a g i n e a t o t a l of N T p e r t u r b e r s in a s p h e r i c a l v e s s e l of r a d i u s R 0 ,
c e n t r e d a b o u t t h e r a d i a t i n g a t o m . The p r o b a b i l i t y of f i n d i n g a p e r t u r b e r
in t h | s p h e r i c a l . s h e l l d e f i n e d by R and R + dR i s 4TR 2 dR3N T /(47rR 3 0 ) =
3 N T R d R / R 0 . T h u s we h a v e t h a t
R d R (14)
Р(Ди) o c I j ( | r / i i)
1
0 Aw
w h e r e R j i s t h e p o s i t i o n of i - t h p e r t u r b e r , a n d t h e i n t e g r a t i o n i s o v e r t h o s e
positions which yield the c o r r e c t p e r t u r b a t i o n Au. The i n t e g r a l can,
h o w e v e r , be w r i t t e n in s u c h a f o r m t h a t i t g o e s o v e r a l l s p a c e w i t h the u s e
of a D i r i c h l e t f a c t o r
J s i n (xd(Au)) e i ň x dx
whe r e
i
Г2 == ^ Y , v ( R i )
" л и
i-1
T h i s f a c t o r t a k e s t h e v a l u e я w h e n fî = 0, i . e . w h e n the t o t a l f r e q u e n c y
d i s p l a c e m e n t i s A u , and i s z e r o e l s e w h e r e ; s c a l a r a d d i t i v i t y h a s b e e n
a s s u m e d at t h i s p o i n t . We m a y t h e r e f o r e w r i t e
R
o Ro
P(Au)dAu = 3 J . . . . J ГR
Г -r-,2
; R „2
;... R „2
N _ d R i d R 2 • • • dR N
o o о
s i n (xd(Au)) e iňx
R
/ \N T °
f _3 > T
( -53-J
: d(Au) J \J R' dReinKJX/"| e"ix^dx
VR 0 -OO 0
IAEA-SMR-12/4,5 141
It i s c o n v e n i e n t to i n t r o d u c e t h e f u n c t i o n
R»
U(x) = f ( 1 - e i V ( R ) x / n ) R 2 dR (15)
0
i n w h i c h c a s e we h a v e
Р(Ды) = / (1 - 3 U ( X ) / R q ) N t e" i x A w dx (16)
Next we allow N T and R 0 to t e n d to i n f i n i t y , with the c o n d i t i o n t h a t

N T / 3 7tR 0 = N. T h i s i s r e a d i l y a c h i e v e d by m e a n s of t h e e x p r e s s i o n
lim ( 1 - 3U(x)/R3 f T
= l i m ( l - 4TTU(X)N/N X ) N T = E " 4 Ï Ï U ( X ) N
We t h e r e f o r e h a v e
CO
, Г -4nU(x)N -ixAw
Р(Ди) = / e e dx
T h e i n t e g r a l m a y b e e x p r e s s e d in a m o r e c o n v e n i e n t f o r m by w r i t i n g
4?rU(x)N = A(x) + i B ( x ) (17)
Then, r e c a l l i n g that U(-x) = U*(x),we obtain
I (Au) ос Р(Ды) = / e _ A ( x ) c o s { B ( x ) + х Д ы } dx (18)
2. Q U A N T U M T H E O R Y O F COLLISION BROADENING
2.1. General formulation
W e t u r n now t o a n e x p o s i t i o n of t h e q u a n t u m t h e o r y of c o l l i s i o n
b r o a d e n i n g . It i s i m p o r t a n t at t h e o u t s e t to u n d e r s t a n d t h e e s s e n t i a l
d i f f e r e n c e s b e t w e e n t h e c l a s s i c a l and q u a n t u m t r e a t m e n t s of t h e p r o b l e m .
We c o n s i d e r q u a n t u m e f f e c t s i n t h e p e r t u r b i n g and r a d i a t i n g a t o m s s e p a r a t e l y .
The i n t e r a c t i o n between t h e m i s a l r e a d y in effect t r e a t e d quantum-
m e c h a n i c a l l y i n t h e c l a s s i c a l t h e o r y , f o r V(R) c a n be t h e r e s u l t of a
q u a n t u m c a l c u l a t i o n , p r o v i d e d both s t a t e s of t h e r a d i a t o r c a n b e c o n s i d e r e d
s t a t i o n a r y on t h e t i m e s c a l e of a c o l l i s i o n .
F i r s t we e x a m i n e w h e t h e r t h e p a t h of a p e r t u r b e r r e l a t i v e to a r a d i a t o r
c a n be a d e q u a t e l y d e s c r i b e d by a c l a s s i c a l o r b i t . The r e l e v a n t p a r a m e t e r
h e r e i s t h e r a t i o of t h e de B r o g l i e w a v e l e n g t h of the a t o m to t h e m i n i m u m
i n t e r a t o m i c d i s t a n c e . T h i s l a t t e r q u a n t i t y i s d e f i n e d s i m p l y by t h e i m p a c t
p a r a m e t e r f o r the c r i t i c a l "Weisskopf" phase change. C l o s e r collisions,
of c o u r s e , o c c u r , but s i n c e t h e y c a u s e l a r g e r t h a n c r i t i c a l p h a s e c h a n g e s
i n t h e r a d i a t i o n , t h e e x a c t p h a s e c h a n g e and t h e d e t a i l s of t h e c o l l i s i o n
142 H I N D MARSH
have no e f f e c t on t h e line p r o f i l e . The condition f o r the c l a s s i c a l p a t h

a p p r o x i m a t i o n to b e v a l i d f o r m o s t c o l l i s i o n s i s , then,
<K p o r
l b c (3MkT)i/2 < < : Pc
(As we have a l r e a d y pointed out, t h i s i s a l s o the condition which e n s u r e s
t h a t t h e path i s s t r a i g h t . ) Taking the w o r s t c a s e , we have to d e a l with
e x p e r i m e n t s at a t e m p e r a t u r e of, say, 2 0 K with h e l i u m a s the p e r t u r b e r .
F o r t h i s c a s e t h e condition b e c o m e s
p » 3 A
It i s quite p o s s i b l e f o r t h i s condition not to be v e r y w e l l s a t i s f i e d , although
m o s t e x p e r i m e n t s a r e c a r r i e d out at t e m p e r a t u r e s of at l e a s t s e v e r a l
h u n d r e d Kelvin, in which c a s e no d i f f i c u l t y a r i s e s . F o r c o m p l e t e g e n e r -
ality, h o w e v e r , t h e q u a n t u m d e s c r i p t i o n of t h e c o l l i s i o n o r b i t s m u s t be
u s e d . When b r o a d e n i n g i s due to e l e c t r o n s t h e s a m e s i t u a t i o n a r i s e s .
Secondly, t h e q u e s t i o n a r i s e s w h e t h e r t h e use of the c l a s s i c a l e l e c t r o n
o s c i l l a t o r r a t h e r t h a n a r e a l a t o m to d e s c r i b e the e m i s s i o n o r a b s o r p t i o n
of r a d i a t i o n i s s a t i s f a c t o r y . It i s well known t h a t t h i s s i m p l e c l a s s i c a l a t o m
c o r r e s p o n d s c l o s e l y to a r e a l a t o m with only two e n e r g y l e v e l s , o r w h e r e
the two e n e r g y l e v e l s involved in the t r a n s i t i o n c o n c e r n e d a r e c o m p l e t e l y
uncoupled f r o m a l l o t h e r l e v e l s . E x c e p t w h e r e t h e r e i s d e g e n e r a c y , o r ,
what a m o u n t s to the s a m e thing, w h e r e the c o l l i s i o n i t s e l f c a u s e s t r a n s i t i o n s
b e t w e e n e n e r g y l e v e l s of t h e r a d i a t o r , we e x p e c t t h i s a p p r o x i m a t i o n to be
v e r y good. Two kinds of d e g e n e r a c y a r e c o n c e r n e d ; one i s the u n i v e r s a l
d e g e n e r a c y a s s o c i a t e d with t h e q u a n t u m n u m b e r m , and the o t h e r the m u c h
r a r e r a c c i d e n t a l d e g e n e r a c y w h e r e l e v e l s with d i f f e r e n t v a l u e s of o t h e r
q u a n t u m n u m b e ' r s have the s a m e , o r n e a r l y t h e s a m e , e n e r g y . If c o l l i s i o n -
i n d u c e d t r a n s i t i o n s o c c u r , we e x p e c t t h a t not only w i l l t h e d a m p i n g c o n s t a n t
of the line be c h a n g e d , but a l s o t h e s h a p e will no l o n g e r be L o r e n t z i a n .
T h i s i s c l e a r f r o m the c l a s s i c a l analogue, in which the c o l l i s i o n s c a u s e
coupling b e t w e e n the o s c i l l a t i o n c o n c e r n e d and o t h e r m o d e s of o s c i l l a t i o n
of the s y s t e m .
The q u a n t u m - m e c h a n i c a l analogue of E q . (2) i s
I(w) ô(io-u l f ) | < f | d | i > | 2 p. (19)

if
w h e r e the i n i t i a l and f i n a l s t a t e s |i)> and | f У a r e the t i m e - d e p e n d e n t s t a t e
f u n c t i o n s r e f e r r i n g to t h e whole s y s t e m of r a d i a t o r s and p e r t u r b e r s .
ô (u - u i f ) i s the D i r a c 6 - f u n c t i o n , which t a k e s the v a l u e 1 when ш = u. f
and i s z e r o e l s e w h e r e ; p t i s t h e n u m b e r d e n s i t y of r a d i a t o r s in the s t a t e
J i)>, and d i s t h e e l e c t r i c dipole m o m e n t .
No f u r t h e r p r o g r e s s c a n be m a d e without i n t r o d u c i n g | i > and |f)>
e x p l i c i t l y . At t h i s point we abandon a wholly g e n e r a l t r e a t m e n t , and
invoke t h e c l a s s i c a l p a t h a p p r o x i m a t i o n .
2.2. The c l a s s i c a l path a p p r o x i m a t i o n
We b e g i n by w r i t i n g the H a m i l t o n i a n f o r the c o m p l è t e s y s t e m a s
H = HA + H p + V
IAEA-SMR-12/4,5 143
w h e r e H A , H p and V a r e r e s p e c t i v e l y the H a m i l t o n i a n s f o r the r a d i a t i n g

a t o m , t h e p e r t u r b e r s and t h e i n t e r a c t i o n b e t w e e n t h e r a d i a t o r and p e r t u r b e r s ,
and the w a v e f u n c t i o n f o r t h e s y s t e m a s
* ( t ) = X(t) Ф (t) (20)
w h e r e x(t) and $(t) a r e r e s p e c t i v e l y the t i m e - d e p e n d e n t w a v e f u n c t i o n s f o r

the r a d i a t o r and the p e r t u r b e r s ; x(t) d e p e n d s on t h e c o - o r d i n a t e s of t h e
r a d i a t o r only and ф(t) on t h o s e of the p e r t u r b e r s only. T h i s w a v e f u n c t i o n
i g n o r e s t h e i n t e r a c t i o n b e t w e e n r a d i a t o r and p e r t u r b e r s , and t h i s i n f l u e n c e
m u s t be e v a l u a t e d by p e r t u r b a t i o n t h e o r y . The w a v e f u n c t i o n d e s c r i b i n g
the m o t i o n of the p e r t u r b e r s o b e y s t h e t i m e - d e p e n d e n t S c h r ö d i n g e r e q u a t i o n
d<Mt)
m dt
H p <Mt)
To find t h e e q u a t i o n obeyed by x(t), we m u l t i p l y E q . (20) by </>*(t) and i n t e g r a t e

over the p e r t u r b e r c o - o r d i n a t e s x :
X(t) = Ф Ю Ф * (t) d x D
f r o m w h i c h we obtain
d X ( t ) _
0 ( t ) H p * * ( t ) d x „ + / (HA + H + v)4>(tW4t)dxB (21)
dt
= [H A + v(t) ] x(t)
where
v(t) = / ф* (t) V(t)dx (22)
We c a n t h e r e f o r e p r o c e e d a s though the a t o m i c wave f u n c t i o n x(t) i s s u b j e c t

to a t i m e - v a r y i n g p e r t u r b a t i o n g i v e n by v(t), and in t h e c l a s s i c a l - p a t h
a p p r o x i m a t i o n (that i s with the ф{t) a s s u m e d to be l o c a l i z e d wave p a c k e t s )
v(t) i s g i v e n s i m p l y by the c l a s s i c a l p o t e n t i a l d e s c r i b i n g the r a p i d l y v a r y i n g
i n t e r a c t i o n b e t w e e n the r a d i a t o r and p e r t u r b e r s .
T h e e f f e c t of the p e r t u r b e r s m a y then be t a k e n into a c c o u n t by w r i t i n g
a t i m e - d e v e l o p m e n t o p e r a t o r T^ w h i c h a c t s on the p e r t u r b e d a t o m i c w a v e
f u n c t i o n x(t) and i s d e f i n e d by
[HA + v(t)]TA(t)
As in the c l a s s i c a l t r e a t m e n t we w o r k in terms of the a u t o c o r r e l a t i o n

f u n c t i o n $ ( s ) , and we s e e t h a t the q u a n t u m m e c h a n i c a l a n a l o g u e of E q . (3) i s
Ks) | d T A ( t , s ) | f f > < f f | d T*(t, s ) | a > + c. c. (23)

Z[<
w h e r e TA (t, s) = TA (t + s) - T A (t), a l a b e l s the u p p e r s t a t e s and a the l o w e r
s t a t e s of the a t o m i c t r a n s i t i o n , t h e a v e r a g e i s t a k e n o v e r a l l t i m e s t and c . c .
144 H I N D MARSH
s t a n d s f o r c o m p l e x c o n j u g a t e . T o c l a r i f y s t i l l f u r t h e r t h e a n a l o g y w i t h the
c l a s s i c a l e x p r e s s i o n , we s e p a r a t e the t i m e - d e p e n d e n t f r o m the t i m e -
i n d e p e n d e n t f a c t o r s , and w r i t e $ ( s ) in t h e e x p a n d e d f o r m
>(s) <a|d|a><ß|d|b><b|TA(t, s)|a><a|T*(t,s)|8> +c.c. (24)

abaß
If t h e r e i s only a s i n g l e u p p e r s t a t e | a^> and a s i n g l e l o w e r s t a t e

i n v o l v e d , ' t h e r e i s only one t e r m in t h e s u m m a t i o n and (24) r e d u c e s to
Ф(в) = | < a | d | û r > 12 [<O|T* (t, s ) | o - > < a | T A (t, s ) | a > + c . c . ] (25)
w h i c h , a p a r t f r o m a n u m e r i c a l f a c t o r , i s e q u i v a l e n t to E q . (3).
It i s c o n v e n i e n t f o r f u r t h e r d e v e l o p m e n t to w o r k with t h e t i m e - e v o l u t i o n
o p e r a t o r in an i n t e r a c t i o n r e p r e s e n t a t i o n . W e w r i t e
U(0, s) = exp ( i H A s / t i ) T ( 0 , s)
T h i s i s p r e c i s e l y a n a l o g o u s to t h e d e v i c e of w o r k i n g with Sř(s)e" lw ° s in t h e
c l a s s i c a l t r e a t m e n t . We then have
m f = exp ( i H A s / t l ) v ( s ) e x p ( - i H A s / î l ) U = v ' ( s ) U
T h i s e q u a t i o n i s s o l v e d by the s t a n d a r d p e r t u r b a t i o n e x p a n s i o n
S S Î!
,
U(0, s) = 1 - (i/ti) fv'(s1)ds1 + (i/bf Jv'(s1)ds1fv {s2)ds2 + ...
o o o
w h i l e i n t e r m s of U(s) t h e c o r r e l a t i o n f u n c t i o n b e c o m e s
i(Es Eb)t/n
Ks) = ^ < a | d | o r > < 0 | d | b > e " < a | u * ( t , s ) | ß > + c . c .
abaß
(26)
2.3. The impact approximation
T h e c a l c u l a t i o n of t h e a v e r a g e in t h e i m p a c t a p p r o x i m a t i o n f o l l o w s
v e r y c l o s e l y t h e c l a s s i c a l c a l c u l a t i o n . T h e c h a n g e ДФ(в) in ®(s) i s w r i t t e n
down; it i n v o l v e s A [ U ( t , s ) ] t w h i c h i s e v a l u a t e d w i t h t h e u s e of the i m p a c t
a p p r o x i m a t i o n , n a m e l y t h a t t h e two f a c t o r s i n A l U ( t , s ) ] t =
[U(t, s)(U(t, s + Д в ) - l ) ] t a r e s t a t i s t i c a l l y i n d e p e n d e n t , and t h a t the p h a s e
c h a n g e s a r e c a u s e d by s u c c e s s i v e c o l l i s i o n s . J u s t a s in t h e c l a s s i c a l c a s e
t h e l i n e p r o f i l e i s L o r e n t z i a n p r o v i d e d t h e r e i s no o v e r l a p p i n g of l i n e s ,
and t h e d a m p i n g c o n s t a n t and s h i f t a r e given by
OO
7 = 2ïtNv f { 1 - e'"1'^ cosfrij - щ)} pdp (27)

о
IAEA-SMR-12/4,5 145
ß = 2 t N v J е'^'Ъ sin(r)i - rj f ) pdp (28)

о
where
< a | S a>
(29)
<»|S
and
v'is^dSj
ß v'(s2)ds2 + . . (30)
i s t h e p e r t u r b a t i o n e x p a n s i o n of t h e S - m a t r i x , d e f i n e d by
S = U(oo, - co)
In t h e s e e x p r e s s i o n s , /л r e p r e s e n t s i n e l a s t i c and r) e l a s t i c (phase changing)

c o l l i s i o n s . If the i n e l a s t i c c o l l i s i o n s a r e i g n o r e d , ц = 0, and t h e e x p r e s s i o n s
f o r 7 and ß r e d u c e to t h o s e obtained with the use of c l a s s i c a l t h e o r y . In
t h i s c a s e the p h a s e c h a n g e s c a n b e c a l c u l a t e d without r e s o r t to p e r t u r b a t i o n
theory.
T h e n e g l e c t of i n e l a s t i c c o l l i s i o n s is c e r t a i n l y j u s t i f i a b l e f o r f o r e i g n -
g a s b r o a d e n i n g w h e r e t h e e n e r g y l e v e l s of t h e r a d i a t i n g a t o m a r e so f a r
s e p a r a t e d t h a t the f r e q u e n c i e s p r e s e n t in the c o l l i s i o n , of the o r d e r of the
r e c i p r o c a l of the d u r a t i o n of the collision, a r e s m a l l e r than t h o s e which
c o r r e s p o n d to the e n e r g y - l e v e l s e p a r a t i o n s . S c h u l l e r and O k s e n g o r n (1969)
have i n v e s t i g a t e d the c a s e of t h e alkali a t o m s with t h e i r f i n e - s t r u c t u r e
d o u b l e t s , but have c o n c l u d e d t h a t the i n e l a s t i c c o l l i s i o n s c a u s e a s i g n i f i c a n t
c o n t r i b u t i o n to the b r o a d e n i n g and s h i f t only i n t h e c a s e of l i t h i u m . T h e
f u n d a m e n t a l r e a s o n f o r t h i s i s t h a t , although the c r o s s - s e c t i o n f o r i n e l a s t i c
c o l l i s i o n s i s quite l a r g e f o r t r a n s i t i o n s between c e r t a i n f i n e - s t r u c t u r e
c o m p o n e n t s , i t i s , e x c e p t f o r l i t h i u m , s i g n i f i c a n t l y s m a l l e r than t h a t f o r
p h a s e c h a n g e s of o r d e r unity ( i . e . t h e Weisskopf c r o s s - s e c t i o n ) .
The s i t u a t i o n i s quite d i f f e r e n t f o r b r o a d e n i n g by e l e c t r o n s . H e r e
i n e l a s t i c c o l l i s i o n s a r e o f t e n of d e c i s i v e i m p o r t a n c e , s i n c e the d u r a t i o n
of t h e c o l l i s i o n s i s m u c h s m a l l e r a s a r e s u l t of the m u c h h i g h e r t h e r m a l
v e l o c i t y of t h e e l e c t r o n s . In t h e c a s e of h y d r o g e n l i n e s , w h e r e t h e b r o a d e n i n g
by the e l e c t r o n i s s u p e r i m p o s e d on the e f f e c t of the q u a s i - s t a t i c f i e l d of the
i o n s , o v e r l a p p i n g of l i n e s o c c u r s a l s o , and r e c o u r s e m u s t be m a d e to
E q . (26).
If f o r t h i s o r any o t h e r r e a s o n t h e l i n e s of a s p e c t r u m o v e r l a p , E q s (27)
and (28) f o r 7 and ß a r e no l o n g e r v a l i d . O f f - d i a g o n a l e l e m e n t s of t h e
S - m a t r i x n e e d to be c a l c u l a t e d , and the m a t r i x f o r the whole s y s t e m of
o v e r l a p p i n g l e v e l s d i a g o n a l i z e d . The line p r o f i l e s a r e not L o r e n t z i a n , n o r
in g e n e r a l a r e they s i m p l y the s u m of the L o r e n t z i a n p r o f i l e s of e a c h c o m -
ponent in the o v e r l a p p i n g s y s t e m . L i t t l e d e t a i l e d e x p e r i m e n t a l o r t h e o r e t i c a l
i n v e s t i g a t i o n of such c a s e s h a s b e e n c a r r i e d out f o r n e u t r a l - a t o m b r o a d e n i n g
but m u c h m o r e h a s b e e n done f o r b r o a d e n i n g by c h a r g e d p a r t i c l e s .
146 HIND MARSH
3. INVERSE P O W E R AND L E N N A R D - J O N E S P O T E N T I A L S
3.1. The impact approximation
With the a s s u m p t i o n s of t h e i m p a c t a p p r o x i m a t i o n , c l a s s i c a l c o l l i s i o n -
b r o a d e n i n g t h e o r y , and a l s o q u a n t u m t h e o r y if c o l l i s i o n - i n d u c e d t r a n s i t i o n s
a r e i g n o r e d , s h o w s t h a t the s p e c t r a l l i n e will a l w a y s be L o r e n t z i a n i n s h a p e ;
t h e h a l f - i n t e n s i t y width and s h i f t , h o w e v e r , a r e s e n s i t i v e to t h e c h o i c e of
p o t e n t i a l . R e c a l l i n g the r e s u l t s of s e c t i o n 1, we have
7 = NvOj
and
ß = NVOi
w h e r e crr and Oj a r e given by E q s (5) and (6).

How the v a l u e s of 7 and ß depend on V(R) i s e x a m i n e d below.
(a) C o n s i d e r V(R) = ± C p R p . F o r t h i s g e n e r a l i n v e r s e - p o w e r p o t e n t i a l ,
i n t e g r a t i o n of E q . (10) by p a r t s y i e l d s t h e r e s u l t
f r o m w h i c h i t f o l l o w s that
, \ 2/(p -1) r -|2/(p-l) . N
and
= [ш]
ст. = a. t a n - ^ Ц - (32)
1 г P_1
p r o v i d i n g t h a t p > 3. The sign of crr i s a l w a y s p o s i t i v e ; t h e sign of ст4

i s t h e s a m e a s t h a t of V(R). C l e a r l y t h e n , the r a t i o \ß/y\ i s t a n (7г/(p - 1)).
T h e c o n n e c t i o n b e t w e e n W e i s s k o p f 1 s s i m p l i f i e d t r e a t m e n t , which g i v e s
a z e r o s h i f t , and t h e m o r e d e t a i l e d r e s u l t s of the L i n d h o l m - F o l e y t r e a t m e n t
d e s c r i b e d h e r e , m a y be u n d e r s t o o d r e a d i l y . W e i s s k o p f a s s u m e s only s t r o n g
c o l l i s i o n s to be e f f e c t i v e (that i s , c o l l i s i o n s f o r which rj > 1 r a d i a n , and
p < po. w h e r e n(p 0 ) = 1) a n d n e g l e c t s e n t i r e l y the e f f e c t of w e a k c o l l i s i o n s .
Now f o r a s t r o n g c o l l i s i o n , c o s rj(p) and s i n rj(p') a r e r a p i d l y o s c i l l a t i n g
f u n c t i o n s which a v e r a g e a p p r o x i m a t e l y to z e r o . T h u s , s t r o n g c o l l i s i o n s
give y x 7rNvpp and ß ~ 0. T h e w e a k , d i s t a n t c o l l i s i o n s , on t h e o t h e r hand,
c a u s e s m a l l p h a s e s h i f t s , s o t h a t c o s n ( p ) ~ 1 and sinr)(p) ~ rj(p); f r o m this it
f o l l o w s t h a t y ~ 0 and ß ~ 27rNv<r)X w h e r e <(г)У i s t h e m e a n p h a s e s h i f t
o c c u r r i n g b e t w e e n two s t r o n g c o l l i s i o n s . C l o s e c o l l i s i o n s , t h e n , c a u s e
m o s t of t h e b r o a d e n i n g of t h e line and the d i s t a n t c o l l i s i o n s a r e r e s p o n s i b l e
f o r the s h i f t .
(b) C o n s i d e r V(R) = - C 6 R . Substitution of p = 6 and t h e a s s u m p t i o n of
t h e n e g a t i v e s i g n in (a) l e a d s i m m e d i a t e l y to the e x p e c t e d b r o a d e n i n g and
s h i f t f o r a v a n - d e r - W a a l s p o t e n t i a l so that
, 2/5 3/5
7 = 4.08 (C 6 /tl) v N
and
ß = -2.96 ( C 6 / î ï ) 2 / V / 5 N
IAEA-SMR-12/4, 5 147
and t h e r a t i o 2 T / ß = - 2 . 8 . It w a s in f a c t t h e f a i l u r e of m a n y o b s e r v a t i o n s
to p r o d u c e a r a t i o i n e v e n a p p r o x i m a t e a g r e e m e n t w i t h t h i s w h i c h l e d s o m e
i n v e s t i g a t o r s to e x p l o r e t h e p o s s i b i l i t i e s of t h e L e n n a r d - J o n e s p o t e n t i a l ,
(c) C o n s i d e r V(K) = C 1 2 R " 1 2 - C 6 R " 6 . T h e L i n d h o l m - F o l e y t h e o r y i n t h e
i m p a c t a p p r o x i m a t i o n w a s d e v e l o p e d f o r the L e n n a r d - J o n e s (12, 6)
p o t e n t i a l by B e h m e n b u r g (1964) and i n d e p e n d e n t l y by H i n d m a r s h , P e t f o r d
and S m i t h (1967). H e r e w e h a v e
. _ 6 3 7Г С12 л . п 37Г Сб -5
ч(р)
" 256 " Т К "
ч 2/5
7 = 4* NV 3 / 5 (С 6 / Ü ) 2 / 5 В (а) (33)
and
\ 2/5
/я V 3 / 5
ß = 2ТГ ( I L ) т (С6 /П)2/5 S(«) (34)
7
f o l l o w i n g t h e n o t a t i o n of H i n d m a r s h e t a l . , w i t h
B ( a ) = / x s i n 2 { | ( a x " n -x" 6 )} dx (35)
S (a) = / x s i n {QX" 11 - x 5} dx (36)

о
and
\ll/5
63тг / 8 _6/5,6/5 _ , Ul/5
« = 7ГГ7Г I •=— J Vv TF
TL C . _J C/ С, .' (37)
256 V 3 7Г/ " 12 / 6
T h e f u n c t i o n s B(A) and S(A) a r e t a b u l a t e d b y t h e s e a u t h o r s f o r a w i d e r a n g e

of v a l u e s of a ; we show t h e m h e r e i n g r a p h i c a l f o r m i n F i g . 1, a l o n g w i t h
t h e f u n c t i o n (1/2)S(û')/B(Q'), w h i c h i s t h e r a t i o ß / y . In o r d e r to i n t e r p r e t
e x p e r i m e n t a l r e s u l t s in t e r m s of a (12, 6 ) - p o t e n t i a l , t h i s l a t t e r c u r v e i s
u s e d w i t h t h e e x p e r i m e n t a l r a t i o to d e t e r m i n e a a n d h e n c e S (a) and B ( A ) .
T h e n , w i t h the. u s e of e i t h e r of t h e m e a s u r e d v a l u e s -y/N o r ß / N , C 6 and C 1 2
a r e found b y a s t r a i g h t f o r w a r d c a l c u l a t i o n . U n f o r t u n a t e l y , t h e o s c i l l a t o r y
c h a r a c t e r of t h e f u n c t i o n s S and В s o m e t i m e s l e a d s to a m b i g u o u s r e s u l t s ,
a l t h o u g h i t i s o f t e n p o s s i b l e to d e d u c e the a p p r o p r i a t e p a i r of c o n s t a n t s .
(d) F i n a l l y w e c o n s i d e r V^R) = C 1 2 R" 12 - Cg R" 8 - C 6 R"6 . T h e e f f e c t
of t h e d i s p e r s i o n t e r m - C 8 R h a s b e e n i n v e s t i g a t e d by H i n d m a r s h , du
P l e s s i s a n d F a r r (1970). T h e p h a s e s h i f t f u n c t i o n b e c o m e s
„ ( P ) = Ü l l £12 - n _ 5» Ç a -7 . Çj g
256 îlv P 16 tiv P
8 "hv
Hence
/ 3 \2/ 5
3 / 5
= 4 N V (С6/Й)2/БВ(АГ,?) (38)
148 H1NDMARSH
a n d
4 2/5
ß = 2ТГ [2fJ NV 3 / 5 (C 6 /tl) 2 / 5 S ( e . Ç) (39)
where
B ( a , I) = / X sin2 l ( o x " u - ? x " 7 - x " 5 ) d x (40)
and
S ( a , i ) = J X s i n ( a x " 1 1 - f x " 7 - x" 5 )dx (41)

0
(42)
Since it i s c l e a r l y i m p o s s i b l e to deduce a l l t h r e e c o n s t a n t s f r o m t h e two

m e a s u r e d q u a n t i t i e s 7 and ß, H i n d m a r s h et a l . u s e a t h e o r e t i c a l m e t h o d
f o r e v a l u a t i n g the p a r a m e t e r c 8 / c j ^ 5 f o r e a c h c a s e i n v e s t i g a t e d , u s i n g a s
a b a s i s t h e w o r k of D a v i s o n (1968), and r e q u i r i n g only t h e k n o w l e d g e of
t h e q u a n t u m n u m b e r s n* and Í f o r the two s t a t e s i n v o l v e d in t h e t r a n s i t i o n .
T h e n f o r a g i v e n f , t h e f u n c t i o n s S and В c a n be c o m p u t e d and t h e c o n s t a n t s
C 6 and C 1 2 d e d u c e d e x a c t l y a s i n (c).
Lo
9,O «
FIG.l. F u n c t i o n s B(ot) and S ( a ) versus logu, a .
IAEA-SMR-12/4,5 149
3.2. The q u a s i - s t a t i c a p p r o x i m a t i o n
In t h i s a p p r o x i m a t i o n the i n t e n s i t y of r a d i a t i o n at any f r e q u e n c y i s
p r o p o r t i o n a l to the p r o b a b i l i t y of o c c u r r e n c e of that f r e q u e n c y . Including
the e f f e c t of m u l t i p l e i n t e r a c t i o n s (with the a s s u m p t i o n of s c a l a r additivity
of the f r e q u e n c y p e r t u r b a t i o n s ) t h e r e s u l t of t h e s e c a l c u l a t i o n s i s given
by B q . (18). We now apply t h i s r e s u l t to s o m e s p e c i f i c i n t e r a t o m i c
potentials.
(a) V(R) = ± C p R" p . P r o v i d e d t h a t p > 3, we have, u s i n g E q s (15) and (17),
47TN 3/Р
A(x) + iB(x) = exp Ь * { 2 - - (Ср/*) г(1Л |x|3/p
p/J
a r e s u l t o b t a i n e d by p a r t i a l i n t e g r a t i o n . F u r t h e r p r o g r e s s r e q u i r e s the
c h o i c e of a s p e c i f i c v a l u e f o r p, u n l e s s we c o n f i n e o u r a t t e n t i o n to the wing
of the l i n e . In t h i s c a s e we need c o n s i d e r the n e a r e s t - n e i g h b o u r i n t e r a c t i o n
only. If then t h e f r e q u e n c y p e r t u r b a t i o n Ди = u - u 0 i s c a u s e d by a single
p e r t u r b e r at R, t h e i n t e n s i t y in t h e r a n g e u, to + du m a y be equated to t h e
p r o b a b i l i t y of finding a lone p e r t u r b e r in t h e r e g i o n R, R + dR.
Thus
3+p
I(Au)dAu oc R 2 dR к | Д и | P
dAu (43)
(b) V(R) = - C 6 R~6 . T h e i n t e g r a l 1(Ды) now t a k e s the v a l u e 0 if u i s

p o s i t i v e (since all p e r t u r b a t i o n s a r e to low f r e q u e n c i e s ) and t h e v a l u e
1(Ди) (С 6 /-Ц) 1 / 2 ы|Ди|" 3 / 2 exp [ - 4 ? r C 6 N 2 / 9R] Ди |] (44)
if Ди i s n e g a t i v e .
T h e i n t e n s i t y m a x i m u m o c c u r s at
2
A i W - f ^ N (45)
showing t h a t the q u a s i - s t a t i c s h i f t i s p r o p o r t i o n a l to the s q u a r e of the

p e r t u r b e r d e n s i t y f o r a v a n - d e r - W a a l s i n t e r a c t i o n . (This c o n t r a s t s with
t h e l i n e a r d e p e n d e n c e of t h e i m p a c t s h i f t . ) On t h e high f r e q u e n c y side of
t h e m a x i m u m the i n t e n s i t y drop i s p r e d o m i n a n t l y e x p o n e n t i a l ; in the f a r
l o w - f r e q u e n c y wing t h e v a r i a t i o n i s p r o p o r t i o n a l to Ди
(c) V(R) = C 1 2 R " 1 2 - C 6 R" 6 . T h e m o r e d i f f i c u l t p r o b l e m of c a r r y i n g
out the q u a s i - s t a t i c t h e o r y f o r a L e n n a r d - J o n e s p o t e n t i a l w a s f i r s t solved
by B e r g e o n , Robin, and V o d a r (1952) and B e r g e o n (1954), who r e s t r i c t e d
t h e i r c a l c u l a t i o n s to the r e g i o n of high p e r t u r b e r d e n s i t y b e c a u s e of c o m p u -
t a t i o n a l d i f f i c u l t i e s . R e c e n t l y t h i s w o r k h a s b e e n extended by F a r r and
H i n d m a r s h (196 8) to t h e l o w - d e n s i t y r e g i o n .
A s b e f o r e , t h i s w o r k i s done with the a s s u m p t i o n t h a t t h e i n d i v i d u a l
f r e q u e n c y p e r t u r b a t i o n s m a y be added s c a l a r l y . It i s c o n v e n i e n t to d e s c r i b e
the p o t e n t i a l in t e r m s of i t s r a d i u s and depth p a r a m e t e r s , cr and e
respectively, where
<r= ( C 1 2 / C 6 ) 1 / 6 , e = iCg/C12
150 HIND MARSH
and t h e n to w o r k i n t e r m s of t h e r e d u c e d v a r i a b l e s
t 2 = 4 e x , r) = Дсо/4е, 5 = TTNCT3/3
If we d e f i n e a f u n c t i o n
-l
A'(x) + iB'(x) = [ A(x) + iB(x)]6
it i s p o s s i b l e to w r i t e E q . (18) in the f o r m
I (Ли) = I t e"6A'Ct) c o s { 6 B ' (t) + nt2} dt
apart f r o m a constant factor.

T h e f u n c t i o n A' (t) + iB'(t) i s given by
00
A'(t) + i B ' ( t ) = - t ^ ^ j t k +
k=0
-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3
T)
FIG.2. l o g I ( n ) versus т]. ( a ) f o r & = 0 . 0 1 ;
IAEA-SMR-12/4,5 151
T h e i n t e g r a l 1(Ди) c o n v e r g e s only slowly, e s p e c i a l l y at low v a l u e s of

p e r t u r b e r d e n s i t y (low 6), and c a n only be e v a l u a t e d a f t e r a lengthy n u m e r i c a l
c o m p u t a t i o n , d u r i n g which it i s n e c e s s a r y to u s e an a s y m p t o t i c a p p r o x i m a t i o n
f o r A and В at l a r g e v a l u e s of t . T h e p r o f i l e s c o m p u t e d by H i n d m a r s h et a l .
a r e shown in F i g s 2(a), (b) and (c). V e r y r e c e n t l y M a h a n (1972) h a s
found an a n a l y t i c a l e x p r e s s i o n f o r t h e l o w - d e n s i t y a p p r o x i m a t i o n . T h e
m o s t n o t e w o r t h y f e a t u r e of t h i s c a l c u l a t i o n i s t h a t at low 6, s a t e l l i t e b a n d s
a p p e a r on t h e l o w - f r e q u e n c y wing at f r e q u e n c i e s c o r r e s p o n d i n g to u 0 - e ,
u0 - 2 e , T h e y a r e , of c o u r s e , h e r e p r e d i c t e d to be m u c h s h a r p e r
t h a n t h e o b s e r v e d s a t e l l i t e f e a t u r e s , a s no i m p a c t b r o a d e n i n g i s i n c l u d e d
in t h e c a l c u l a t i o n .
H o w e v e r , it i s c l e a r t h a t the a p p e a r a n c e of t h e s e b a n d s , at l e a s t in
s o m e c a s e s , i s a p u r e l y s t a t i s t i c a l p h e n o m e n o n , a r i s i n g f r o m the f a c t t h a t
the p o t e n t i a l g o e s t h r o u g h a m i n i m u m at an e n e r g y c o r r e s p o n d i n g to a
f r e q u e n c y of u 0 - e .
-0.6 -0.5 -0.Д -Ü3 -0.2 -0.1 0.0 0.1 0.2 0.3
ÎI
BIG. 2. ( c o n t ' d ) (b) for 6 = 0 . 0 2 ;
152 HIND MARSH
3.3. General theory
T h e d i f f i c u l t i e s i n h e r e n t i n a t h e o r y of p r e s s u r e b r o a d e n i n g , which
d e s c r i b e s t h e s h i f t , width and shape of a s p e c t r a l l i n e u n d e r a l l c o n d i t i o n s
and which i s not s u b j e c t to the r e s t r i c t i o n s of e i t h e r the i m p a c t o r q u a s i -
s t a t i c a p p r o x i m a t i o n s , a r e s u c h that no g e n e r a l a n a l y t i c a l e x p r e s s i o n f o r
the line s h a p e c a n be found. An a p p r o x i m a t e solution i s a c h i e v e d if t h e
following a s s u m p t i o n s a r e m a d e :
(1) T h e a t o m i c r a d i a t i o n s u f f e r s f r e q u e n c y c h a n g e s , and t h e r e f o r e p h a s e
c h a n g e s , a s a r e s u l t of c o l l i s i o n s b e t w e e n r a d i a t o r s and p e r t u r b e r s .
(2) P e r t u r b e r s , w h i c h a r e d i s t r i b u t e d r a n d o m l y i n s p a c e , follow s t r a i g h t
p a t h s with c o n s t a n t v e l o c i t y r e l a t i v e to the o p t i c a l l y a c t i v e a t o m s .
(3) T h e d u r a t i o n of a c o l l i s i o n i s p r o p o r t i o n a l to t h e i m p a c t p a r a m e t e r .
(4) F r e q u e n c y p e r t u r b a t i o n s c a u s e d by c o l l i s i o n s which o v e r l a p in t i m e
a r e additive.
(5) T h e p h a s e c h a n g e s u f f e r e d during a c o l l i s i o n i s t a k e n to be a l i n e a r
f u n c t i o n of t i m e . T h i s i s equivalent to a p p r o x i m a t i n g t h e c o m p l i c a t e d
t i m e d e p e n d e n c e of Au(t) by a c o n s t a n t f r e q u e n c y change d u r i n g t h e
collision.
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6

T]
FIG. 2 . ( c o n t ' d ) (c) for 6 = 0 . 0 6 .

IAEA-SMR-12/4, 5 153
The t i m e - a v e r a g e d phase change i s written a s
i ! , ( t , s )
[e ] = e-G(s) + iK(s)
in which c a s e the i n t e n s i t y d i s t r i b u t i o n m a y b e w r i t t e n , f r o m E q s (3) and (4)
I(u) = f e ^ cos{K(s) + (u - u 0 ) s } d s (48)
and it can be shown ( L i n d h o l m 1945) that

о
2
(1 - c o s rjp) (s - T p ) - — sinrip + 2т р
G(s) = ^ Nvop P
00
К p s) - s) - sin s + 2s (49)
•I
+ ; N7a„ (1 - COS (Tp Kp
and
s
ъ
K(s) = ) m a p
v°
(1 - c o s r?p) — + (s - Tp) sin Г]р
p
•^Nvop (1 - c o s к s) — + (т - s) sin к s (50)

Р Kp v
w h e r e f o r a c o l l i s i o n of i m p a c t p a r a m e t e r p, тр i s the c o l l i s i o n t i m e ,
Kp i s the p h a s e c h a n g e p e r unit t i m e during c o l l i s i o n , r]p = к р т р i s t h e
t o t a l p h a s e c h a n g e p e r c o l l i s i o n and crp = 2npůp i s the c r o s s - s e c t i o n f o r
s u c h a c o l l i s i o n . B e h m e n b u r g (1968) h a s e v a l u a t e d t h e s e e x p r e s s i o n s f o r
a L e n n a r d - J o n e s p o t e n t i a l . It should be noted t h a t the a p p r o x i m a t i o n
r e m o v e s a l t o g e t h e r t h e s a t e l l i t e band by i n s i s t i n g on a u n i f o r m r a t e of
c h a n g e of p h a s e .
A d i f f e r e n t a p p r o a c h to t h e p r o b l e m of finding a g e n e r a l t h e o r y h a s
b e e n m a d e by H i n d m a r s h and F a r r (1969). H e r e the s t a r t i n g point i s the
q u a s i - s t a t i c line p r o f i l e , c a l c u l a t e d f o r V(R) = C 1 2 R~ - C g R " 6 , which
h a s a l r e a d y b e e n d i s c u s s e d . U s i n g the f a c t t h a t a F o u r i e r a n a l y s i s of a
f i n i t e wave t r a i n of f r e q u e n c y ы a v e r a g e d o v e r r a n d o m l i f e t i m e s , y i e l d s
a L o r e n t z p r o f i l e with d a m p i n g c o n s t a n t у ( w h e r e 7" 1 i s t h e m e a n l i f e t i m e ) ,
H i n d m a r s h and F a r r give a s an a p p r o x i m a t e e x p r e s s i o n f o r the line shape
(51)
^ - / (0 u - f f l
w h e r e y(w')" 1 i s t h e m e a n d u r a t i o n of wave t r a i n s of f r e q u e n c y u 1 , and

Is (W) i s t h e q u a s i - s t a t i c i n t e n s i t y d i s t r i b u t i o n . (The c o n t i n u o u s change
i n u 1 , a s a p e r t u r b e r f l i e s p a s t an o p t i c a l l y a c t i v e a t o m , i s not, of c o u r s e ,
s t r i c t l y e q u i v a l e n t to a s e q u e n c e of v a l u e s of u' l a s t i n g f o r f i n i t e d u r a t i o n s . )
154 H I N D MARSH
F o r t h e p u r p o s e of c a l c u l a t i n g I(u) the l i n e i s d i v i d e d i n t o two m a i n

r e g i o n s , the i m p a c t r e g i o n w h e r e the q u a s i - s t a t i c calculation i s invalid,
and t h e q u a s i - s t a t i c r e g i o n w h e r e I s ( u ' ) f o r m s a s a t i s f a c t o r y s t a r t i n g p o i n t
f o r the c a l c u l a t i o n of t h e p r o f i l e . T h e b o u n d a r y b e t w e e n t h e s e two r e g i o n s
on the l o w - f r e q u e n c y wing o c c u r s at u g , w h e r e u g m a y be e s t i m a t e d a s
d e s c r i b e d i n E q . (11). T h e c o n t r i b u t i o n to I(u) f r o m w > u g (note t h a t wg < u 0 )
i s c a l c u l a t e d by t a k i n g I s (co')du' w i t h i n t h e i m p a c t r e g i o n and g i v i n g i t a
L o r e n t z i a n d i s t r i b u t i o n of w i d t h 2y and s h i f t ß c a l c u l a t e d a c c o r d i n g t o
H i n d m a r s h e t a l . (1967) f o r t h e p a r t i c u l a r i n t e r a c t i o n p o t e n t i a l u n d e r
c o n s i d e r a t i o n . Since t h e q u a s i - s t a t i c i n t e n s i t y o n t h e h i g h - f r e q u e n c y w i n g
i s v e r y low, i t m a y b e s e t e q u a l to z e r o , so t h a t t h e l i n e s h a p e I(u) i s
g i v e n by t h e e x p r e s s i o n
T h e m e a n l i f e t i m e s a s s o c i a t e d with t h e f r e q u e n c i e s u ' < и a r e e s t i m a t e d

o n t h e b a s i s of an i d e a a d v a n c e d by K u h n and L o n d o n (1934), n a m e l y t h a t
t h e t i m e - v a r y i n g f r e q u e n c y w(t) of a c o n t i n u o u s l y p e r t u r b e d w a v e t r a i n m a y
b e c o n s i d e r e d t o r e m a i n u(0) f o r so l o n g a s t h e p h a s e of u(t) d o e s not d i f f e r
f r o m w(0) by m o r e t h a n s o m e a r b i t r a r y a m o u n t . C h o o s i n g t h i s a m o u n t t o
b e 1 r a d i a n , H i n d m a r s h a n d F a r r d e f i n e t h e s e m i - l i f e t i m e T of t h e f r e q u e n c y
u(0) by t h e c o n d i t i o n
T
w(t)dt - w(0)T = 1
0
T h e n , r e p l a c i n g u(t) b y t h e f i r s t n o n - z e r o t e r m ( t e r m n) i n t h e T a y l o r
e x p a n s i o n of u(t) a b o u t t h e p o i n t t = 0, the c o n d i t i o n f o r T b e c o m e s
-|l/(n+l)
n + 1
(d n u(t)/dt") t =o J
Using this expression, the m e a n lifetimes f o r all f r e q u e n c i e s between

Ug and (Jo - e , w h e r e e i s t h e d e p t h of t h e L e n n a r d - J o n e s p o t e n t i a l , m a y
b e e s t i m a t e d by c o n s i d e r i n g only the a t t r a c t i v e p a r t of t h e p o t e n t i a l ; t h e
m e a n l i f e t i m e f o r t h e f r e q u e n c y uQ - e i s c a l c u l a t e d u s i n g t h e f u l l e x p r e s s i o n
f o r t h e p o t e n t i a l , and t h i s s a m e v a l u e i s u s e d f o r a l l f r e q u e n c i e s l e s s t h a n
u 0 - e ( f u r t h e r out on t h e l o w - f r e q u e n c y w i n g ) . T h i s l a s t a p p r o x i m a t i o n i s
not s e r i o u s a s the low v a l u e of I s (u') in t h i s r e g i o n e n s u r e s t h a t t h e m a j o r
c o n t r i b u t i o n t o I(w) c o m e s f r o m f r e q u e n c i e s g r e a t e r t h a n <Jq - e .
4. A SURVEY O F E X P E R I M E N T A L R E S U L T S F O R N E U T R A L - A T O M
BROADENING
4.1. impact region m e a s u r e m e n t s
4. 1 . 1 . Foreign-gas broadening
It i s , of c o u r s e , i n t h e i m p a c t r e g i o n w h e r e t h e e x p e r i m e n t a l s t u d y
of c o l l i s i o n - b r o a d e n e d s p e c t r a l l i n e s i s m o s t e a s i l y i n t e r p r e t e d q u a n t i t a t i v e l y .
IAEA-SMR-12/4,5 155
With the t h e o r i e s of s e c t i o n 3, it i s p o s s i b l e to d e t e r m i n e two p a r a m e t e r s

of a d i f f e r e n c e p o t e n t i a l . If one of t h e s t a t e s i s a g r o u n d s t a t e , and if the
potential for this state has been determined f r o m elastic scattering m e a s u r e -
m e n t s , t h e b r o a d e n i n g d a t a p r o v i d e the p a r a m e t e r s f o r t h e e x c i t e d s t a t e .
S e v e r a l e x p e r i m e n t a l s t u d i e s of i m p a c t - r e g i o n c o l l i s i o n b r o a d e n i n g
h a v e b e e n i n t e r p r e t e d in t e r m s of a ( 1 2 , 6 ) - i n t e r a c t i o n . T h e f i r s t of t h e s e
w a s B e h m e n b u r g ' s (1964) study of t h e s o d i u m l i n e (3 2 S!/ 2 - 3 P 3 / 2 ) p e r t u r b e d
by h e l i u m and by a r g o n . In t h e c a s e of a r g o n , the s h i f t - t o - b r o a d e n i n g r a t i o
l i e s on t h e o s c i l l a t i n g p a r t of the S ( a ) / 2 B ( a ) c u r v e , and so t h e i n t e r a c t i o n
c o n s t a n t s c a n n o t be d e t e r m i n e d u n a m b i g u o u s l y . In t h e c a s e of h e l i u m , the
m e a s u r e d C 6 of (33 ± 10)X 10" 66 J - c m 6 i s a n o m a l o u s l y l a r g e c o m p a r e d to
t h e t h e o r e t i c a l v a l u e of 2.9 X 10" 66 J - c m 6 , and t h e s h i f t to a l o w e r f r e q u e n c y
i s unusual for this p e r t u r b e r .
Smith (1967) i n v e s t i g a t e d the c a l c i u m i n t e r c o m b i n a t i o n line (4 S 0 - 4 P x )
f o r m e d i n a b s o r p t i o n i n a t m o s p h e r e s of h e l i u m , neon, a r g o n , and k r y p t o n
at t e m p e r a t u r e s of a p p r o x i m a t e l y 1030 К and p e r t u r b e r d e n s i t i e s up to
7 X 10 18 cm" 3 . In a l l c a s e s , i m p a c t r e g i o n c o n d i t i o n s w e r e w e l l s a t i s f i e d
with s h i f t and b r o a d e n i n g v a r y i n g l i n e a r l y with p e r t u r b e r d e n s i t y . The
r e s u l t s w e r e i n t e r p r e t e d using t h e v e r s i o n of H i n d m a r s h e t a l . (1967) of
the L i n d h o l m - F o l e y t h e o r y f o r a (12, 6 ) - p o t e n t i a l .
T h e following i n t e r a c t i o n c o n s t a n t s w e r e obtained:
c6 с
Atom pair
10"66 J - c m 6 10" 109 J-cm12
Ca-He 2.0 ± 0.2 0.97

Ca-Ne 1.8 ± 0.2 1. 1
Ca-Ar 10.8 ± 0 . 8 7.4
Ca-Kr 25 ± 2 54
T h e s e C 6 v a l u e s a r e a l l h i g h e r than t h e t h e o r e t i c a l v a l u e s by a f a c t o r
of about 2, a r e s u l t w h i c h i s a t t r i b u t e d by H i n d m a r s h et a l . (1970) to the
n e g l e c t of h i g h e r - o r d e r d i s p e r s i o n t e r m s in the i n t e r a t o m i c i n t e r a c t i o n
( s e e below).
A s e a r c h i n g t e s t of t h e v a l i d i t y of the (12, 6 ) - p o t e n t i a l i n the i n t e r -
p r e t a t i o n of c o l l i s i o n b r o a d e n i n g w a s applied by Vaughan and Smith (196 8),
who studied t h e r e d l i n e of k r y p t o n (4p 5 ( 2 P 3 / 2 ) 5s 3 / 2 2 - 4p 5 ( 2 P 3 / 2 ) 5p 3/2 2 )
p e r t u r b e d by low p r e s s u r e s of h e l i u m , neon, a r g o n , and k r y p t o n at t e m p e r a -
t u r e s of 80'К and 295 K. T h e y w e r e thus able to t e s t the c o m p l e x t e m p e r a t u r e
d e p e n d e n c e p r e d i c t e d by H i n d m a r s h et a l . a s w e l l a s to m e a s u r e t h e i n t e r -
a c t i o n c o n s t a n t s . T h e s h i f t - t o - b r o a d e n i n g r a t i o s at t h e two t e m p e r a t u r e s
w e r e f i t t e d a s c l o s e l y a s p o s s i b l e to the t h e o r e t i c a l S(a)/2B(a) c u r v e , with
the r e s t r i c t i o n t h a t e a c h p a i r should show the c o r r e c t t e m p e r a t u r e
d e p e n d e n c e . T h e c o r r e s p o n d i n g v a l u e s of S(a) and B(a) w e r e t h e n used
to p r e d i c t t h e t e m p e r a t u r e e f f e c t s in shift and b r o a d e n i n g i n d i v i d u a l l y .
T h e s e a r e c o m p a r e d in the following list:
ся
СП
TABLE I. R E S U L T S O F LOW-DENSITY M E A S U R E M E N T S
Carbon
Helium Neon Argon Krypton Xenon Nitrogen
tetrafluoride
Width Shift Width Shift Width Shift Width Shift Width Shift Width Shift Width Shift
Na 5896 P 1 / 2 0.742 -0.196 0.49 -0.214
5890 P 3 / 2 0.689 -0.213 0.49 -0.223
К 7699 P j / 2 1.01 -0.42 0.82 -0.36
7665 P 3 / 2 1.01 -0.36 0.82 -0.30
К 4047 P 1 / 2 1.45 0.71 2.20 -9.2 1.65 -0.83
4044 P 3 / 2 2.02 0.82 -0.16 2.58 -8.3 1. 89 -1.02
Rb 7947 P 1 / 2 0.595 +0.228 0.627
7800 P 3 / 2 0.735 -0.092 0.855
Rb 4216 P 1 ( i 2 2.77 +0.93 1.30 +0.22 2.21 -1.2 1.51
4202 P 3 / 2 1.88 +0.43 0.73 -0.16 2.56 -1.0 1.01
Cs 8943 P j y 2 +0.128 -0.04 0.30 -0.238 0.28 -0.20 0.49 -0.25 -0.29
8521 P 3 / 2 +0.015 -0.08 0.30 -0.215 0.28 -0.20 0.23 -0.25 -0.23
Cs 4593 P 1 ( / 2 +0.51 -0.70 1.1 - 0 . 62 -0.65

4555 P 3 / 2 +0.26 -0.63 3.2 -0.62 - 0 . 65
AIL units are c m " 1 ( r e l . density) 1 . Additional measurements ate reported by Ch'en et al. foi broadening by krypton in t h e 3rd and 4th Cs doublets, and shifts oř г Р 3 / 2 up to the 20th doublet. Relative
density is defined as the ratio of the actual density of the gas to the density the s a m e gas would have at 0°C and 760 Torr.
IAEA-SMR-12/12 157
Shift at 2 9 5 K / S h i f t at 80К Width at 295 K / W i d t h at 80 К
Perturber Observed Predicted Observed Predicted
He 2.62 2.16 1.87 1.73
Ne 0.93 0.84 1.67 1,70
Ar 2.29 1.79 2.07 1.64
Kr 1.47 1.43 1.48 1.43
In the c a s e of a r g o n a s e r i o u s d i s c r e p a n c y a r i s e s , which Vaughan and

Smith s u g g e s t m a y be due e i t h e r to the i n a d e q u a c y of the t h e o r e t i c a l t r e a t m e n t
f o r p o t e n t i a l s which a r e n e i t h e r d e e p l y a t t r a c t i v e n o r s h a r p l y r e p u l s i v e , o r
to the w r o n g c h o i c e of i n t e r a c t i o n p o t e n t i a l . To t e s t the l a t t e r p o s s i b i l i t y ,
they c a l c u l a t e d the S(or), B ( f f ) - c u r v e s f o r ( 1 0 , 6 ) - and (18, 6 ) - p o t e n t i a l s , but
n e i t h e r m a d e m u c h d i f f e r e n c e in the a r g o n r e g i o n . The o b s e r v e d C 6 - v a l u e s
a r e in s a t i s f a c t o r y a g r e e m e n t with the Unsold c a l c u l a t i o n s :
C6(10"66 J-cm6)
Atom p a i r Observed Predicted
Kr-He 4.5 4.7

Kr-Ne 15.9 8.6
Kr-Ar 24.5 35.4
Kr-Kr 54.6 53.8
T h e study of a l k a l i - m e t a l d o u b l e t s h a s b e e n p u r s u e d s i n c e the e a r l y
d a y s of e x p e r i m e n t a l c o l l i s i o n b r o a d e n i n g ( F u c h t b a u e r a n d ' G o s s l e r , 1933;
W a t s o n and M a r g e n a u , 1933; Hull, 1936; P e t e r m a n , 1933; Ny and
C h ' e n , 1937), and a s t r i k i n g f e a t u r e of all such m e a s u r e m e n t s i s the
e x i s t e n c e of a p p a r e n t l y u n p r e d i c t a b l e d i f f e r e n c e s b e t w e e n c o m p o n e n t s of
the s a m e doublet p e r t u r b e d by the s a m e g a s . S c h u l l e r and O k s e n g o r n (1969)
have shown t h a t t h e 2 P]y 2 c o m p o n e n t b e h a v e s a s in L i n d h o l m ' s t h e o r y , but
f o r the 2 Pg/2 c o m p o n e n t t h e r e i s a v a r i a t i o n due to the a n i s o t r o p y of the
e x c i t e d s t a t e i n t e r a c t i o n . Applying t h e i r c a l c u l a t i o n to the c a s e of the
b r o a d e n i n g of the s o d i u m r e s o n a n c e l i n e s by a r g o n , they find t h a t the
c a l c u l a t e d s h i f t s a r e in good a g r e e m e n t with t h o s e m e a s u r e d by K l e m a n
and L i n d h o l m , but t h a t t h e r e i s a d i s c r e p a n c y in t h e h a l f - w i d t h s . T h e
i n t e r f e r e n c e with the c o l l i s i o n b r o a d e n i n g p r o c e s s by c o l l i s i o n a l e x c i t a t i o n
t r a n s f e r b e t w e e n the f i n e - s t r u c t u r e l e v e l s i s r e g a r d e d by s o m e a u t h o r s a s
being f u n d a m e n t a l to t h i s "problem, and both t h e o r e t i c a l (Callaway and B a u e r ,
1965) and e x p e r i m e n t a l ( K r a u s e , 1966; J o r d a n and F r a n k e n , 1966) e v i d e n c e
shows that t h e c r o s s - s e c t i o n s f o r t h e s e two p r o c e s s e s a r e of c o m p a r a b l e
s i z e . H o w e v e r , S c h u l l e r and O k s e n g o r n (1969) show t h a t t h i s p r o c e s s
h a s a m a r g i n a l e f f e c t , m e a s u r a b l e only in l i t h i u m .
A r e c e n t c o m p r e h e n s i v e study of the p r e s s u r e b r o a d e n i n g of the f i r s t
few l i n e s of the p r i n c i p a l s e r i e s of c a e s i u m by h e l i u m , neon, a r g o n , k r y p t o n .
T A B L E II. POTASSIUM P R I N C I P A L SERIES IN He, A r , AND K r
Helium Argon Krypton
Width Shift Width Shift Width Shift
К 4044 P 3 / 2 7.08 ± 0.2 0.37 ± 0.02 8..0 ±0.1 -2.22 ± 0.03 5.50 ± 0.15 -1.97 t 0.05
К 4047 P1/2 4.94 t 0.04 1.22 i 0.02 7.54 ± 0.05 -1.75 ± 0.08 6.6 ± 0.2 - 1 . 8 4 ± 0.05
Units of ÎO" 2 0 c m " 1 ( c m " 3 ) " 1 .

IAEA-SMR-12/12 159
xenon, and c a r b o n t e t r a f l u o r i d e h a s b e e n u n d e r t a k e n by C h ' e n , G a r r e t t ,

G i l b e r t and c o - w o r k e r s (1966 I, II; 1967 III, IV; 1969 V, VI). M e a s u r e m e n t s
have b e e n m a d e at p r e s s u r e s of up t o 300 a t m in s o m e c a s e s . T h e g e n e r a l
f e a t u r e s of t h e s e r e s u l t s a r e e x p l a i n e d by r e c e n t c l a s s i c a l g e n e r a l t h e o r i e s
(see below). T h e l o w - d e n s i t y m e a s u r e m e n t s , t h e r e s u l t s of w h i c h a r e
s u m m a r i z e d in T a b l e I along with t h e r e s u l t s of s o m e of the e a r l i e r w o r k
m e n t i o n e d above, a r e not i n t e r p r e t e d q u a n t i t a t i v e l y b e c a u s e of s o m e u n u s u a l
f e a t u r e s , which i n c l u d e n o n - l i n e a r i t y of the b r o a d e n i n g - v e r s u s - d e n s i t y c u r v e s
n e a r the o r i g i n and an a p p a r e n t l y v e r y s t r o n g t e m p e r a t u r e e f f e c t on the
b r o a d e n i n g at h i g h e r d e n s i t i e s . T h e r e is a p o s s i b i l i t y t h a t both of t h e s e
e f f e c t s a r e e x p e r i m e n t a l : t h e n o n - l i n e a r i t y a r i s i n g f r o m the u n c o r r e c t e d
e f f e c t of h y p e r f i n e s p l i t t i n g and i n s t r u m e n t a l s l i t width, which a m o u n t to
s o m e 0.6 c m " 1 , and the t e m p e r a t u r e e f f e c t a r i s i n g f r o m a n a l y s i s of l i n e s
w h o s e p e a k a b s o r p t i o n i s in e x c e s s of 50%. T h e r e i s s o m e e v i d e n c e t h a t
h e a v i l y a b s o r b e d p r o f i l e s c a n c a u s e o v e r e s t i m a t e d line w i d t h s ( M c C a r t a n , 1970).
R o s t a s and L e m a i r e (1971) have m e a s u r e d t h e c a e s i u m doublet 6 2 S - 7 2 P
b r o a d e n e d by h e l i u m and a r g o n . T h e s e m e a s u r e m e n t s , m a d e at low p r e s s u r e ,
r e p r e s e n t an i m p r o v e m e n t on t h o s e of C h ' e n and G a r r e t t , and a r e quoted
in T a b l e IV.
M c C a r t a n and H i n d m a r s h (to be p u b l i s h e d ) have m a d e a d e t a i l e d i n v e s t i -
g a t i o n of the s e c o n d doublet of t h e p o t a s s i u m p r i n c i p a l s e r i e s ( ^ S ^ 5 2 P 1 / 2 3 / 2 )
f o r m e d in a b s o r p t i o n in a t m o s p h e r e s of h e l i u m , a r g o n and k r y p t o n u n d e r
s t r i c t i m p a c t - r e g i o n c o n d i t i o n s . T h e r e s u l t s of t h i s study a r e s u m m a r i z e d
in T a b l e II. It w a s found t h a t not a l l of t h e s e could be f i t t e d to the S(a)/2B(a)
c u r v e s , a f a c t which the a u t h o r s a t t r i b u t e to the i n a d e q u a c y of the " s t r a i g h t
p a t h " a p p r o x i m a t i o n in t h e s e c a s e s . The i n t e r a c t i o n c o n s t a n t s d e d u c e d
by M c C a r t a n et a l . a r e
C 6 J- c m 6 C
12 J- c m 1 2
P P P
l/2 P
3/2 l/2 3/2
He - 9.2 X 10" 65 _ 7.6 X 10" 106

Ar - 6.6 X 10~64 - 5.8X 10" 106
64 64 106
Kr 4 . 8 X 10" 4.5 X 10" 1.2 X 10" 2.3 X 10" 106
C o m b i n i n g t h e s e v a l u e s with g r o u n d - s t a t e m e a s u r e m e n t s quoted by
B e r n s t e i n and M u c k e r m a n (1967) we obtain t h e following e x c i t e d - s t a t e
constants:
12
( C 6 'exc J. c m ^ 12 )exc J - c m
P P
l/2 P
3/2 l/2 P
3/2
65
He - 9.5 X 10" - 7.6 X 10 - 1 0 6
Ar - 6.9 X 10" 64 - 5.8 X 10
-106
-106
Kr 6.2 X 10" 64 5.5 X 10" 64 1.4 X 1 0 " " 2.3 X 10
160 HIND MARSH
T h e e x p e r i m e n t a l f a c t s r e g a r d i n g c o l l i s i o n b r o a d e n i n g in a l k a l i d o u b l e t s
m a y be s u m m a r i z e d a s f o l l o w s :
(1) T h e d i f f e r e n c e in s h i f t of the f i n e - s t r u c t u r e c o m p o n e n t s d e p e n d s on
s e r i e s m e m b e r and p e r t u r b e r , not on the n a t u r e of t h e a l k a l i .
(2) W h e r e t h e r e i s a h i g h - f r e q u e n c y s h i f t , t h e 2 P x / 2 c o m p o n e n t i s shifted
m o r e t h a n the 2 P 3( / 2 c o m p o n e n t . The r a t i o i s l a r g e r f o r the f i r s t s e r i e s
m e m b e r than the s e c o n d .
(3) D i f f e r e n c e s in s h i f t s to low f r e q u e n c i e s a r e u s u a l l y s m a l l , and t h e r e
i s a p p a r e n t l y no way of knowing which c o m p o n e n t shows the s t r o n g e r
shift.
(4) T h e b r o a d e n i n g of t h e 2 P 3 / 2 c o m p o n e n t i s n o r m a l l y slightly g r e a t e r
t h a n t h a t of the 2 Р ! / 2 c o m p o n e n t , although e x c e p t i o n s a r e found.
T a b l e III s h o w s , in c o l u m n s f o u r and f i v e , the s o r t of a g r e e r n e n t which

i s found b e t w e e n t h e o r e t i c a l C 6 - v a l u e s and t h o s e deduced f r o m c o l l i s i o n -
b r o a d e n i n g e x p e r i m e n t s using the L i n d h o l m - F o l e y t r e a t m e n t f o r a ( 1 2 , 6 ) -
p o t e n t i a l . On t h e whole, the e x p e r i m e n t a l C 6 - v a l u e s e x c e e d the t h e o r e t i c a l
o n e s by f a c t o r s of about two o r t h r e e . The l a s t c o l u m n s h o w s the e x p e r i -
m e n t a l v a l u e s when a ( 12, 8, 6 ) - p o t e n t i a l i s a s s u m e d . T h e r e i s in g e n e r a l
an i m p r o v e m e n t , which l e n d s s u p p o r t to the i d e a t h a t h i g h e r t e r m s in the
d i s p e r s i o n i n t e r a c t i o n (R~8 , R" 10 . . . ) m a y not be n e g l i g i b l e in the e x c i t e d
T A B L E III. COMPARISON O F E X P E R I M E N T A L AND T H E O R E T I C A L

C6-VALUES
C6 experimental
10"65 J - c m 6
C6 theoretical
Author Line Perturber
1 0 " 65 J. c m 6 , ( 1 2 , 6) ( 1 2 . 8, 6)
(1) C a 6573 He 0.062 0.2 ±0.02 0.10 ± 0.02
(1) Ca 6573 Ne 0.113 0.18 ± 0.02 0.10 ± 0.02
(1) Ca 6573 Ar 0.46 1.08 ± 0.08 0.23 ± 0.02
(1) C a 6573 Kr 0.70 2.53 ± 0.2 0.61 ± 0.06
(2) C a 4227 He 0.30 0.3 ±0.1 0.18 ± 0.06
(3) Ar 6965 Ar 2.4 9 ±4 2.9 ± 3
(4) К 4047 Kr 38.1 52 ± 15 30 ±9
(5) Sr 4607 Ar 2.62 4.3 ±0.4 2.8 ±0.8
(6) Kr 7 6 0 1 He 0.47 0.45 ± 0.09 0.36 ± 0.07
(6) Kr 7 6 0 1 Ne 0.86 1.59 ± 0.3 0.81 ± 0.15
(6) Kr 7 6 0 1 Ar 3.54 2.45 ± 0 . 5 1.05 ± 0.2
(6) Kr 7 6 0 1 Kr 5.38 5.46 ± 1.1 4.4 ± 1
(1) S m i t h ( 1 9 6 7 ) ; (2) H i n d m a i s h ( 1 9 5 9 ) ; (3) H i n d m a r s h , T h o m a s ( 1 9 6 1 ) ; (4) M c C a l t a n ,

Hindmarsh (1969); (5) F a i r , H i n d m a r s h ( 1 9 7 1 ) ; (6) V a u g h a n , S m i t h ( 1 9 6 8 ) .
IAEA-SMR-12/12 161
T A B L E IV. COMPARISON O F C s LINE R E S U L T S
Experiment Theory
Cs l i n e Gas Rostas, L e m a i r e Roueff
(1971) (1970)
X 4593 2 y/N 8.8 ±0.5 9.2
62S1/2 - 7 2 P l / 2 He e/N +1.5 ±0.1
2y/6 + 5 . 85 +6.3
X 4555 2 y/N 6.9 ±0.4
2 2 +0.73 ± 0.05
6 Sl/2 - 7 Рз/г He ß/N
2 y/ß +9.45
X 4593 2 y/N 6.7 ±0.5 4.9
62S1/Z- 72Pl/2 Ar ß/N -1.63 ±0.05
2 у/В -4.1 -11. 6
X 4555 2 y/N 5.8 ±0.3
Z 2 -1.55 ± 0.06
6 S l / 2 - 7 P3/2 Ar ß/N
2 y/ß -3.74
2 y / N and e / N a r e in units of 10 " 2 ° c m " ' / c m " 3 .
s t a t e . F i n a l l y , the c a l c u l a t i o n s of Roueff (1970) have b e e n c o m p a r e d with

e x p e r i m e n t by R o s t a s and L e m a i r e (1971) f o r the c a e s i u m line X 4593
( 6 2 S 1 / 2 _ 7 2 P i / 2 ) b r o a d e n e d by h e l i u m and a r g o n . The c a l c u l a t i o n s , which
do not i n c l u d e s p i n - o r b i t i n t e r a c t i o n , a r e not e x p e c t e d to apply to t h e o t h e r
c o m p o n e n t of the d o u b l e t , X 4555, which w a s , h o w e v e r , a l s o m e a s u r e d .
T a b l e IV c o m p a r e s the r e s u l t s of R o s t a s and L e m a i r e with the c a l c u l a t i o n
of R o u e f f , and shows the a g r e e m e n t to be highly s a t i s f a c t o r y .
4.1.2. Resonance broadening
R e s o n a n c e - b r o a d e n i n g c a l c u l a t i o n s in the i m p a c t a p p r o x i m a t i o n p r e d i c t
that p u r e r e s o n a n c e - b r o a d e n e d l i n e s a r e L o r e n t z i a n in s h a p e with a h a l f -
i n t e n s i t y width in r a d i a n - s " 1 of
i
Z 7 ( 5 á }
V \2j' + 1 / mw 0
w h e r e N i s the a t o m d e n s i t y , fjj- and u 0 "the o s c i l l a t o r s t r e n g t h and a n g u l a r

f r e q u e n c y , r e s p e c t i v e l y , of the r e s o n a n c e line, and j, j' a r e the a n g u l a r -
m o m e n t u m q u a n t u m n u m b e r s of the g r o u n d s t a t e and r e s o n a n c e s t a t e ,
r e s p e c t i v e l y . The width i s i n d e p e n d e n t of t e m p e r a t u r e , and t h e s h i f t i s
p r e d i c t e d to be z e r o . (See the r e v i e w of r e s o n a n c e b r o a d e n i n g by Kuhn and
Oî
to
T A B L E V. DENSITY D E P E N D E N C E O F LINE BROADENING
2 y / N at 80 К 2y/ti at 280 К 6/N

Element Â Transition
10cm-'(cm*3)"' ÎO" 2 0 c m " 1 ( c m " 3 ) " 1 10"20 c m " 1 ( c m ' 3 ) " 1
He 1281 2'P! - 3 ' S 0 7.85 ± 0.4 8.1 ± 0.6 0 ± 0.1
6678 2'P, - 3 ' D , 7.8 ±0.4 7.9 ± 0 . 5 0 ± 0.05
Ne 6678 4 - 2P< 6.27 ± 0.15 6.2 ± 0.3 0 ± 0.1
At 7503 'Pi - 2 Pi 15.66 ± 0 . 7 15.0 ± 0.7 0 ± 0.2
7514 ' P i - 2P5 3.6 ±0.3 3.9 ± 0.4 0.07 ± 0.03
Кг 7685 'Pi - V 10.8 ± 0.5 11.0 ± 0 . 6 0 ± 0.5
7587 3 5
Pi * P 12.8 ± 0.2 13.1 ± 0 . 6 0.1 ± 0 . 1
IAEA-SMR-12/12 163
L e w i s (1969).) T h e v a l u e of t h e c o n s t a n t kjj. d e p e n d s on j, j' and the

a p p r o x i m a t i o n s m a d e in the c a l c u l a t i o n . Some r e c e n t v a l u e s a r e :
k
l/2.3/2
k k k k
o,i l/2, 3/2 l/2,1/2 l/2,1/2
Ali, G r i e m (1965, 1966) 1 1 1 1.00
O m o n t , M e u n i e r (1968) 1.04 - - -
Stacey, C o o p e r (1969) 1.04 1.04 0.903 1.15
B e c a u s e of the d i f f i c u l t i e s of s e l f - a b s o r p t i o n in e m i s s i o n l i n e s , m o s t
m e a s u r e m e n t s m a d e d i r e c t l y on r e s o n a n c e l i n e s ( l a r g e l y in the c a s e of
alkali m e t a l s ) h a v e b e e n m a d e in a b s o r p t i o n . M o s e r and Schulz (1959) have
t a b u l a t e d the e x p e r i m e n t a l r e s u l t s a v a i l a b l e at t h a t t i m e , and d i s c r e p a n c i e s
a m o u n t i n g to s e v e r a l o r d e r s of m a g n i t u d e o c c u r b e t w e e n d i f f e r e n t e x p e r i -
m e n t s and b e t w e e n e x p e r i m e n t and t h e o r y . Since t h e n , Y a ' a k o b i (1966, 1968)
h a s m a d e m e a s u r e m e n t s on the r e s o n a n c e l i n e s of l i t h i u m , but t h e s e r e s u l t s
a l s o s e e m to be not v e r y q u a n t i t a t i v e .
A m o r e a c c u r a t e t e c h n i q u e i n v o l v e s t h e i n d i r e c t study of the b r o a d e n i n g
of a r e s o n a n c e l e v e l by m a k i n g m e a s u r e m e n t s on an e m i s s i o n line w h o s e
l o w e r s t a t e i s t h e r e s o n a n c e l e v e l . Q u a n t i t a t i v e r e s u l t s w e r e f i r s t obtained
t h i s way by H i n d m a r s h and T h o m a s (1961), who i n v e s t i g a t e d the s e l f -
b r o a d e n i n g i n a r g o n and w e r e able to e s t i m a t e t h e o s c i l l a t o r s t r e n g t h of
the r e s o n a n c e line X 1048 by studying the s e l f - b r o a d e n i n g of the line X 8264.
L e w i s , Ř e b b e c k , and Vaughan (1969) adopted the s a m e m e t h o d and m e a s u r e d
t h e r e s o n a n c e b r o a d e n i n g of t h e 4 2 P s t a t e s of p o t a s s i u m by studying i n
e m i s s i o n the l i n e s (4 2 P 1 / 2 3 / 2 - n 2 S 1 / 2 , n = 6, 7, 8). T h i s gave the v a l u e s
k = 3 k = 1 2 4 3 w i t h t h e r a t i к
l/2,3/2 ^ ^ i °- ' l/2,l/2 " ± °- ' ° 1/2,3/г/к1/2,1/2 =
1.09'± 0.06. Kuhn and h i s c o - w o r k e r s (Kuhn, Vaughan, 1964; Kuhn,
L e w i s , 1967; Vaughan, 1966a, b, 1968; S t a c e y , Vaughan, 1964) have m a d e
a m a j o r i n v e s t i g a t i o n of r e s o n a n c e b r o a d e n i n g in the i n e r t g a s e s h e l i u m ,
neon, a r g o n , and k r y p t o n u s i n g t h i s i n d i r e c t t e c h n i q u e , with the o b j e c t of
t e s t i n g the r e s u l t s of t h e o r y . In all c a s e s studied the v a r i a t i o n of h a l f -
width with d e n s i t y w a s v e r y c l o s e to l i n e a r o v e r a d e n s i t y r a n g e of
10 16 - 4X 10 17 c m " 3 . The r e s u l t s obtained f o r l i n e s l e a d i n g to the u p p e r
s t a t e of a s t r o n g r e s o n a n c e line a r e given in T a b l e V.
In all c a s e s t h e r e i s l a r g e b r o a d e n i n g , no m e a s u r a b l e s h i f t and no
m e a s u r a b l e t e m p e r a t u r e e f f e c t . O t h e r l i n e s w e r e m e a s u r e d which a r e
t r a n s i t i o n s to a w e a k r e s o n a n c e l e v e l , and t h e s e show 5 - 1 0 t i m e s s m a l l e r
b r o a d e n i n g , an i n c r e a s e of b r o a d e n i n g with t e m p e r a t u r e and a n o n - z e r o
s h i f t ; in t h e s e l i n e s a h i g h e r - o r d e r i n t e r a c t i o n i n t e r f e r e s with the r e s o -
nance broadening.
An i n t e r e s t i n g p h e n o m e n o n h a s shown up in t h e s e r a r e - g a s e x p e r i m e n t s ,
n a m e l y t h a t the L o r e n t z width e x t r a p o l a t e d to z e r o d e n s i t y i s s i g n i f i c a n t l y
h i g h e r than the e x p e c t e d n a t u r a l width. T h i s " e x t r a p o l a t i o n a n o m a l y " h a s
b e e n e x p l a i n e d by Kuhn, L e w i s , and Vaughan (1965) i n t e r m s of an a d d i t i o n a l
coupling width.
1 6 4 HIND MARSH
RELATIVE DENSITY OF ARGON
FIG.3. C a e s i u m l i n e shift versus r e l a t i v e argon d e n s i t y .
4.2. Non-impact region measurements
Since M i n k o w s k i (1935) f i r s t showed t h a t t h e i n t e n s i t y d i s t r i b u t i o n i n

t h e f a r l o w - f r e q u e n c y wing of t h e s o d i u m r e s o n a n c e l i n e s p e r t u r b e d by
a r g o n w a s of t h e GJ" 3/ ' 2 -form, n u m e r o u s e x p e r i m e n t s h a v e p r o v i d e d d a t a
c o n c e r n i n g t h e n o n - i m p a c t r e g i o n of p r e s s u r e b r o a d e n i n g ; we d i s c u s s h e r e
only a few of t h e m o r e r e c e n t of t h e s e .
G r a n i e r and h i s c o - w o r k e r s have p r e s e n t e d , i n a s e r i e s of p a p e r s
(1961, 1963, 1 9 6 5 a , 1966a, b), the r e s u l t s of a s t u d y of t h e i n f l u e n c e
of p e r t u r b e r m a s s and t e m p e r a t u r e on t h e b r o a d e n i n g and s h i f t of t h e
r e s o n a n c e l i n e s of m e r c u r y and the a l k a l i m e t a l s at high p e r t u r b e r d e n s i t y ,
and h a v e c o m e to the c o n c l u s i o n t h a t , e s p e c i a l l y w h e n d e a l i n g with l i g h t
a t o m s , r e p u l s i v e f o r c e s c a n n o t b e n e g l e c t e d . T h i s r e s u l t , of c o u r s e ,
p a r a l l e l s t h e w o r k of B e h m e n b u r g and H i n d m a r s h i n t h e i m p a c t r e g i o n .
C h ' e n 1 s w o r k h a s b e e n i n t e r p r e t e d by B e h m e n b u r g (196 8), who h a s
c o n s i d e r e d t h e e f f e c t s of b o t h n e o n and a r g o n . F i g u r e s 3 and 4 s h o w ,
IAEA-SMR-12/12 165
RELATIVE DENSITY OF ARGON
FIG.4. C a e s i u m l i n e h a l f - i n t e n s i t y w i d t h versus r e l a t i v e a r g o n d e n s i t y .
r e s p e c t i v e l y , t h e s h i f t and t h e h a l f - i n t e n s i t y width of t h e c a e s i u m l i n e
(6 2 S Q - 6 2 Р 1 ( , 2 ) a s a f u n c t i o n of r e l a t i v e d e n s i t y of a r g o n ( d e n s i t y r e l a t i v e
to t h a t at N. T . P . ) o b t a i n e d e x p e r i m e n t a l l y by C h ' e n and c a l c u l a t e d by
B e h m e n b u r g . The C 6 and C 1 2 v a l u e s u s e d in t h e c a l c u l a t i o n a r e o b t a i n e d
by B e h m e n b u r g f r o m t h e l o w - d e n s i t y m e a s u r e m e n t s ( c o r r e c t e d f o r t h e
e f f e c t s of h y p e r f i n e s t r u c t u r e and s l i t width) u s i n g the w e l l - e s t a b l i s h e d
(12, 6) i m p a c t t h e o r y .
M c C a r t a n et a l . h a v e , in c o n t r a s t to C h ' e n , s t u d i e d a l o w - f r e q u e n c y
wing p r o f i l e at low p e r t u r b e r d e n s i t y , but at s u c h l a r g e d i s p l a c e m e n t s
f r o m t h e u n p e r t u r b e d l i n e t h a t t h e i m p a c t t h e o r y i s no l o n g e r a p p l i c a b l e .
U s i n g t h e t h e o r y of H i n d m a r s h et a l . , t h e y h a v e i n t e r p r e t e d t h e s h a p e of
t h e (4 2 S 1 y 2 - 5 2 P 1 / 2 ) a b s o r p t i o n l i n e of p o t a s s i u m b r o a d e n e d by k r y p t o n a s
a r i s i n g f r o m a (12, 6 ) - i n t e r a c t i o n p o t e n t i a l w h e r e
e = 27 ± 1 cm" 1
CT = (8.0 ± 0.3) X 10" 8 c m

166 HIND MARSH
which i s in e x c e l l e n t a g r e e m e n t with t h e i m p a c t r e g i o n r e s u l t that
e = 25 ± 2 cm" 1
a = (8.0 ± 0.3) X 10" 8 c m
F i g u r e 5 s h o w s t h a t t h e c a l c u l a t e d and e x p e r i m e n t a l p r o f i l e s a r e in v e r y
good a g r e e m e n t o v e r an i n t e n s i t y r a n g e of at l e a s t f o u r o r d e r s of m a g n i t u d e ,
including the p r o m i n e n t s a t e l l i t e band at about 25 cm" 1 f r o m the c o r e . The
c o n t r i b u t i o n to the p r o f i l e beyond the band i s a l m o s t e n t i r e l y due to " i m p a c t "
b r o a d e n i n g of t h e band i t s e l f , due to the f i n i t e d u r a t i o n of the wave t r a i n s
a b s o r b e d at t h a t f r e q u e n c y . T h e r e i s s o m e i n d i c a t i o n of a f e a t u r e at about
50 c m " 1 , which would be e x p e c t e d on the b a s i s of t h e q u a s i - s t a t i c c a l c u l a t i o n
of F a r r e t a l . (1968) which p r e d i c t s s a t e l l i t e s at 2, 3 . . .
FIG.5. E x p e r i m e n t a l i n t e n s i t y d i s t r i b u t i o n of t h e p o t a s s i u m l i n e a t X 4047 Â in an a t m o s p h e r e of k r y p t o n
(red wing). T h e solid l i n e is t h e p r e d i c t e d s h a p e using e = 27 c m " 1 and о = 8 Â. P o s i t i o n in c m " 1 r e l a t i v e
to t h e u n p e r t u r b e d l i n e .
IAEA-SMR-12/12 167
T h i s w o r k h a s r e m o v e d any s e r i o u s doubt a s to t h e n a t u r e of t h e a l k a l i -
r a r e - g a s l o w - f r e q u e n c y b a n d s , of which a g r e a t n u m b e r of o b s e r v a t i o n s
have b e e n m a d e and s e v e r a l t h e o r i e s a d v a n c e d . The e s s e n t i a l e x p e r i m e n t a l
f a c t s about s u c h b a n d s , a l l of which a r e c o n s i s t e n t with t h e t h e o r y of
H i n d m a r s h et a l . , a r e a s follows:
(1) S a t e l l i t e s a r e m o r e l i k e l y to be o b s e r v e d t h e h i g h e r the p o l a r i z a b i l i t y
of t h e p e r t u r b e r s ( i . e . the l a r g e r the v a l u e of a d ) .
(2) At high p r e s s u r e s t h e b a n d s b e c o m e d i f f u s e and d i s a p p e a r .
(3) T h e p o s i t i o n of t h e s a t e l l i t e r e l a t i v e t o t h e m a i n line i s a l m o s t i n d e -
p e n d e n t of p r e s s u r e and t e m p e r a t u r e ( s e e , f o r e x a m p l e , G r a n i e r and
G r a n i e r , 1966c).
(4) T h e b a n d s a r e usually s e v e r a l wave n u m b e r s wide e v e n at low p r e s s u r e s ,
but t h e i n t e n s i t y d r o p s s h a r p l y on the l o w - f r e q u e n c y side of t h e s a t e l -
l i t e . In g e n e r a l , t h e m o r e d i s t a n t the band the m o r e d i f f u s e it i s .
T h e r e m a i n i n g f e a t u r e of f o r e i g n - g a s - b r o a d e n e d s p e c t r a l l i n e s which
i s to b e d i s c u s s e d i s the a p p e a r a n c e , usually at high p e r t u r b e r d e n s i t y ,
of s a t e l l i t e b a n d s on the h i g h - f r e q u e n c y wing of a c o l l i s i o n - b r o a d e n e d l i n e .
M o s t w o r k on t h i s topic h a s b e e n c a r r i e d out on the r e s o n a n c e l i n e s of
xenon, m e r c u r y , and t h e a l k a l i m e t a l s . T h e m a i n f e a t u r e s of t h e s e b a n d s a r e :
(1) They a r e fainter than low-frequency bands.

(2) T h e h e a v i e r t h e p e r t u r b e r , t h e c l o s e r the h i g h - f r e q u e n c y band i s to
t h e m a i n line, although in g e n e r a l they a r e m u c h f u r t h e r f r o m t h e
l i n e c e n t r e than l o w - f r e q u e n c y b a n d s .
(3) F o r a g i v e n a t o m p a i r , t h e h i g h - f r e q u e n c y band s e p a r a t i o n i s l e s s
f o r h i g h e r m e m b e r s of t h e p r i n c i p a l s e r i e s , and low s e r i e s m e m b e r s
u s u a l l y show a second, f a i n t e r band.
(4) S t r u c t u r e i s o c c a s i o n a l l y o b s e r v e d (Robin, 1957).
(5) T h e p o s i t i o n of t h e h i g h - f r e q u e n c y band a p p e a r s to be t e m p e r a t u r e and
p r e s s u r e d e p e n d e n t ( B e s o m b e s et a l . , 1969).
C h ' e n and W i l s o n (1961) and C h ' e n , Atwood and W a r n o c k (1961) give

a c o m p r e h e n s i v e s u r v e y of band p o s i t i o n s .
T h e t h e o r e t i c a l u n d e r s t a n d i n g of the h i g h - f r e q u e n c y s a t e l l i t e b a n d s
i s so f a r v e r y i n c o m p l e t e . T h e p o s s i b i l i t y t h a t , like the l o w - f r e q u e n c y
b a n d s , they a r i s e f r o m t u r n i n g p o i n t s in t h e d i f f e r e n c e p o t e n t i a l c a n n o t
be r u l e d o u t . T h e d i f f i c u l t y i s t h a t r a t h e r l i t t l e i s known about t h e d e t a i l e d
shape of t h e i n t e r a t o m i c p o t e n t i a l at t h e c l o s e d i s t a n c e s which m u s t be
r e s p o n s i b l e f o r t h e f o r m a t i o n of h i g h - f r e q u e n c y b a n d s .
5. BROADENING BY CHARGED P A R T I C L E S
5.1. B r o a d e n i n g t h r o u g h the q u a d r a t i c S t a r k e f f e c t
T h i s type of b r o a d e n i n g o c c u r s in a p l a s m a w h e r e both i o n s and e l e c t r o n s

a r e p r e s e n t . We b e g i n by m a k i n g s o m e e s t i m a t e s of the m a g n i t u d e s of the
w i d t h s c a u s e d by both t y p e s of p e r t u r b e r i n a t y p i c a l p l a s m a w h e r e the
e l e c t r o n v e l o c i t y i s 5 X 1 0 7 c m • s ' 1 and t h e ion v e l o c i t y 2 X 10 5 c m • s " 1 .
168 HIND MARSH
The e l e c t r o n d e n s i t y we t a k e to be 10 15 cm" 3 . It i s e a s y to show f r o m

E q . (31) t h a t
7 = 11.4 (C 4 /Ti) 2 / 3 v 1 / 3 N e (54)
f o r t h e R" 4 i n t e r a c t i o n which h o l d s h e r e . (We a r e at t h i s s t a g e i g n o r i n g

i n e l a s t i c c o l l i s i o n s . ) T h u s we find, with C 4 = 1СГ39 e r g - c m 4 , that
7 — 5 X 10 10 r a d • s" 1 = 0 . 3 c m " 1 f o r e l e c t r o n s while f o r i o n s
7 ~ 5X 10 9 r a d • s" 1 = 0.03 cm" 1 . We have a l r e a d y shown in s e c t i o n 1 t h a t
the i m p a c t r e g i o n e x t e n d s to 10 14 rad • s" 1 f o r e l e c t r o n s and to 5 X 10 10 r a d • s" 1
f o r i o n s i n t h e s e c o n d i t i o n s . We conclude, t h e r e f o r e , t h a t such a s p e c t r a l
line s u f f e r s i m p a c t b r o a d e n i n g by both e l e c t r o n s and i o n s , the f o r m e r being
m u c h the m o r e i m p o r t a n t . If, h o w e v e r , Ne i s i n c r e a s e d by a f a c t o r of
10 to 10 16 cm" 3 , q u a s i - s t a t i c b r o a d e n i n g by the i o n s will s t a r t to be s i g n i f i -
c a n t . Indeed a s y m m e t r y of t h e l i n e s f o r m e d at high e l e c t r o n and ion
densities has often been observed.
We t h u s n e e d an e x p r e s s i o n for the q u a s i - s t a t i c b r o a d e n i n g due to the
i o n s . F o r the f a r wing of the line, f o r m e d by n e a r e s t - n e i g h b o u r i n t e r a c t i o n s
E q . (43) c a n be t a k e n o v e r d i r e c t l y , giving
i i" 7 / 4
I(Au)dAcooc | Д и | dAu (55)
-1/3
Since t h e a v e r a g e d i s t a n c e b e t w e e n the i o n s m u s t be of o r d e r N e it i s
e a s y to s e e t h a t the width of t h e line i s ~ ( C 4 / t l ) N 4 / 3 ~ 10 s r a d • s " 1 . T h i s
i s s m a l l c o m p a r e d with t h e i m p a c t width due to the e l e c t r o n s , but it
i n c r e a s e s m o r e r a p i d l y with i n c r e a s i n g N e . At Ne ~ 10 17 cm" 3 t h e two
b e c o m e c o m p a r a b l e , and g r e a t e r than the i m p a c t b r o a d e n i n g by t h e i o n s .
We c o n c l u d e , t h e r e f o r e , t h a t at low e l e c t r o n d e n s i t y i m p a c t b r o a d e n i n g
by e l e c t r o n s i s the d o m i n a n t influence on the l i n e - w i d t h , but at h i g h e r
d e n s i t i e s q u a s i - s t a t i c b r o a d e n i n g by i o n s b e c o m e s s i g n i f i c a n t . It m u s t
a l s o be n o t i c e d t h a t t h e i m p a c t b r o a d e n i n g by i o n s m a y not a l w a y s be
negligible.
5.2. I n f l u e n c e of i n e l a s t i c c o l l i s i o n s
The e x p r e s s i o n f o r 7 and ß given i n E q s (27) and (28) allow t h e p o s s i b i l i t y

of i n e l a s t i c c o l l i s i o n s , although they involve the c l a s s i c a l p a t h a p p r o x i m a t i o n
f o r the p e r t u r b e r s . A f i r s t a p p r o x i m a t i o n i s not d i f f i c u l t to obtain if we
r e s t r i c t o u r s e l v e s to the c a s e w h e r e only the u p p e r l e v e l s u f f e r s p e r t u r b a t i o n .
In t h i s c a s e we e a s i l y find (by putting /uf = 17 f = 0 in E q s (27) and (28) and
expanding the e x p o n e n t i a l in E q . (29)
7 = 27rN e v J 11 - e"Mi c o s r i i i p d p
0
1
2írNe v / e sin r); • pdp
+ ir) = v
»i i *Ï J '<sl)dsi +
J V ( s 1 ) d s 1 j V ( s 2 )ds 2
IAEA-SMR-12/12 169
Since we a r e dealing with the q u a s i - s t a t i c S t a r k e f f e c t the f i r s t - o r d e r

p e r t u r b a t i o n v a n i s h e s . It i s t h e n e a s y to obtain
(55a)
(56)
A
x x
F(x) = 1 x [e" Ei(x) - e E i ( - x ) ] , Ei(x) = J y dt
w h e r e the s u m m a t i o n s a r e o v e r a l l s t a t e s | s^> of t h e p e r t u r b e d a t o m .
Noticing t h a t C4 = 2 c s , we c a n e a s i l y see the e f f e c t of t h e i n e l a s t i c c o l -
s
l i s i o n s . T h e y a r e u n i m p o r t a n t f o r p » ps and a r e in any c a s e d o m i n a t e d
by t h e i n f l u e n c e of the s t a t e with l a r g e s t p s , t h a t i s the c l o s e s t - l y i n g s t a t e .
A s u m m a t i o n a l s o h a s to be p e r f o r m e d o v e r the S t a r k c o m p o n e n t s of the
s p e c t r a l line c o n c e r n e d .
C a l c u l a t i o n s b a s e d on t h e s e s i m p l e c o n s i d e r a t i o n s a g r e e to within 10%
with m o r e e l a b o r a t e n u m e r i c a l c a l c u l a t i o n s and with o b s e r v a t i o n . C o r r e c t
a v e r a g i n g o v e r the M a x w e l l i a n d i s t r i b u t i o n of v e l o c i t i e s i s of s o m e
importance.
5.3. I n f l u e n c e of the i o n s
W h e r e the i o n s b r o a d e n e n t i r e l y t h r o u g h the q u a s i - s t a t i c e f f e c t all

t h a t i s r e q u i r e d to i n c l u d e t h e i r r e l a t i v e l y s m a l l c o n t r i b u t i o n i s a s i m p l e
folding of the s t a t i c and i m p a c t p r o f i l e s .
5.4. C o m p a r i s o n with e x p e r i m e n t
T a b l e VI s h o w s how t h e s e r e l a t i v e l y s i m p l e c a l c u l a t i o n s a g r e e with
e x p e r i m e n t and with m o r e e l a b o r a t e c a l c u l a t i o n s .
5.5. B r o a d e n i n g t h r o u g h t h e l i n e a r Stark e f f e c t
We now t u r n to t h e p r o b l e m of c a l c u l a t i n g the b r o a d e n i n g of h y d r o g e n -
like l i n e s due to the i o n s and e l e c t r o n s in a p l a s m a . T h i s i s a q u e s t i o n
which r a i s e s a n u m b e r of unique and v e r y d i f f i c u l t p r o b l e m s , and it i s
only p o s s i b l e h e r e to s u m m a r i z e the p r o g r e s s so f a r m a d e .
We have a l r e a d y shown t h a t in any n o r m a l line p r o f i l e the ionic
b r o a d e n i n g w i l l be q u a s i - s t a t i c and t h e e l e c t r o n i c b r o a d e n i n g i s i m p a c t in
c h a r a c t e r . We need t h e r e f o r e to e s t i m a t e t h e m a g n i t u d e s of t h e s e two
-a
О
T A B L E VI. C A L C U L A T E D AND E X P E R I M E N T A L VALUES O F VARIOUS He I LINES
Line c4. N, G r i e m , Kolb, Simple

Experiment
10 ^ 10" T, К Baranger, O e r t e l formulas
(Â)
Â Transition erg-cm4 cm"3 (Â) (Ä)
5016 2 1 S - 3'P -1334 1.65 25 000 6. 5 -4.8 7.2 -6 7.2 -4.7
4713 23P - 43S 1250 1.3 20 000 7 6 7.6 8.9 8.5 5.7
4713 2SP - 4 3 s 1250 0.25 30 000 1. 5 1.5 1.4 1.4 1.5 1.1
s 3
3889 2 S - 3 P 264 1.5 25 000 2 1.2 2.1 1.1 2.7 1
IAEA-SMR-12/12 171
e f f e c t s . T h e q u a s i - s t a t i c p r o b l e m w a s solved long ago by H o l t s m a r k (1919)

and it i s s u f f i c i e n t to quote the r e s u l t
(57)
.^-VJnfl, \cn lV-9Lo/
aß
w h e r e I a 6 i s t h e i n t e n s i t y and ( C 2 ) a g / Z e i s t h e S t a r k c o e f f i c i e n t f o r t h e
S t a r k c o m p o n e n t aß of t h e l i n e , and t h e f u n c t i o n
W(ß) / х s i n x exp - ( x / ß ) 3 / 2 dx (58)
W i t h 2/3
/ \
ZeN2/3
•Ш
E 0 = 2тг[ -h j
Two a p p r o x i m a t e e x p r e s s i o n f o r W(ß) a r e
W(ß) = 1.496 ß"5/2 (1 + 5 . 1 0 7 ß'3/2+ 1 4 . 9 3 ß'3 + .. .) ß » l (59)
W(ß) = 4 ~ ß 2 ( ! - 0.463 ß 2 + 0.1227 ß* - . . . ) ß « 1 (60)

о 71
E q . (59) g i v e s t h e s a m e r e s u l t a s E q . (43) with p = 2 f o r the v e r y f a r wing

of t h e l i n e . T h e o r d e r of m a g n i t u d e of the width i s e a s i l y found without
d e t a i l e d c a l c u l a t i o n s , f o r t h e m e a n d i s t a n c e b e t w e e n t h e i o n s ~ N ; 1 / 3 and
the m e a n p e r t u r b a t i o n i s t h e r e f o r e ~ (C2 /h)N 2 / / 3 in a n g u l a r f r e q u e n c y u n i t s .
Now C 2 ~ e 2 a 0 n ( n - 1) a s we have a l r e a d y pointed out s o t h a t , f o r H 0
and N e = 10 1 5 c m ' 3 , the width of the line i s ~ 10 1 1 r a d - s " 1 , o r 0.5 c m " 1 .
Next we w i s h to e s t i m a t e the m a g n i t u d e of t h e i m p a c t b r o a d e n i n g by
e l e c t r o n s ; E q . (30a) g i v e s f o r t h e c l a s s i c a l p h a s e s h i f t , with p = 2,
the r e s u l t
Ç2
-hv
Therefore
7 = 27rNev 1 - cos pdp = 47rNeV J sin 2 pdp
It i s e a s y to s e e t h a t t h i s i n t e g r a l d i v e r g e s : at l a r g e p t h e i n t e g r a l v a r i e s
a s p'1, t h u s c a u s i n g a l o g a r i t h m i c d i v e r g e n c e a t t h e u p p e r l i m i t . A s i m p l e
way out of t h e d i f f i c u l t y i s to cut off the i n t e g r a l at s o m e u p p e r l i m i t p m .
B e a r i n g in m i n d that the v a l u e of the i n t e g r a l with an u p p e r l i m i t of p0
(the W e i s s k o p f r a d i u s ) i s about ?rp2 Nv we have
172 HIND MARSH
A l o g i c a l c h o i c e f o r p i s the Debye r a d i u s ( k T / 4 î r e 2 N e which m e a s u r e s

t h e d i s t a n c e at which an ion i s shielded f r o m m o r e d i s t a n t e l e c t r o n s by the
i n t e r v e n i n g i o n s . At N e = 10 1 5 c m " 3 , T = 5 0 0 0 K , V - 5 X 1 0 7 c m - s " 1 ,
C 2 = 10" 26 e r g • cm 2 , we find p 0 ~ 3 X 10" 1 c m , p m ~ 1.4 X 10"5 c m . Hence
the p r i n c i p a l c o n t r i b u t i o n to c u r v e s f r o m the s e c o n d t e r m of E q . (61), and
7 ~ 5 X 10 1 0 r a d • s " 1 . T h i s i s c o m p a r a b l e with the s t a t i c c o n t r i b u t i o n due
to the i o n s .
T h e d e t a i l e d c a l c u l a t i o n s a r e e x t r e m e l y involved, and m a n y p o i n t s of
p r i n c i p l e a r i s e . B u t the r e a d e r m u s t r e f e r to the l i t e r a t u r e f o r f u r t h e r
i n f o r m a t i o n . Good s t a r t i n g p o i n t s a r e " P l a s m a S p e c t r o s c o p y " by H . G r i e m
(1964) and c h a p t e r 10 of " i n t r o d u c t i o n to the T h e o r y of A t o m i c S p e c t r a "
by I . I . S o b e l ' m a n (1972).
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IAEA-SMR-12/12
RADIOFREQUENCY SPECTROSCOPY
A. KASTLER
Laboratoire de physique,
Ecole normale supérieure,
Paris, France
Abstract
RADIOFREQUENCY SPECTROSCOPY.
1. Introduction; 2. Special features of RF transitions (Predominance of induced emission ; Electric
dipole transitions and magnetic dipole transitions ; The width and shape of RF lines ; The Doppler width ; The
natural line width; Broadening effects) ; 3 . Short historical survey ; 4 . Production and detection of RF
transitions; The two classes of detection methods: change in the wave properties and change in the properties
of matter (Rabi*s detection method of molecular beams; The optical detection method of RF resonances;
Orientation or polarization and alignment; Atomic orientation and magnetization at thermal equilibrium;
Detection by transfer of angular momentum ; Detection by nuclear physics techniques ; The electronic detection
methods of RF resonances) ; 5. The behaviour of paramagnetic atomic states in a constant field and in a
radiofrequency field (Definitions; Behaviour of an atomic system in a constant field; Behaviour of a collection
of many identical paramagnetic atoms in a constant field ; Behaviour of a collection of atoms in an RF field ;
Classical theory of the motion of a spin submitted to a constant field and an RF field) ; 6 . Results (Study of
pure Zeeman intervals; Fine-structure intervals of the n = 2 l e v e l of the hydrogen a t o m ; Hyperfine-structures
in atomic ground states; Muonium e " / j + ; Positronium e " e + ) ; 7. Conclusions.
1. INTRODUCTION
We u s e f o r r a d i o f r e q u e n c y t h e a b b r e v i a t i o n R F . An e l e c t r o m a g n e t i c
(e. m . ) w a v e c a n b e c h a r a c t e r i z e d b y its f r e q u e n c y v e x p r e s s e d in h e r t z (Hz),
o r by t h e w a v e n u m b e r a = v/c in c m " 1 , or b y t h e w a v e l e n g t h \ = I/o = c/v
i n v e r s e l y p r o p o r t i o n a l t o v. We a l s o u s e t h e " w a v e v e c t o r " к = 2ira and the
c i r c u l a r f r e q u e n c y и = 2nv, a n d w r i t e k= ( u / c ) . We a r b i t r a r i l y l i m i t " H e r t z i a n
w a v e s " at v - 10 1 2 Hz ( I T H z ) , w h i c h c o r r e s p o n d s t o A = 0.30 m m . Higher
f r e q u e n c i e s b e l o n g to t h e i n f r a - r e d s p e c t r u m .
In t h e H e r t z i a n s p e c t r u m we m a y d i s t i n g u i s h c o n v e n t i o n a l l y
Audiofrequencies RF Microwaves
i/ < 1 0 4 Hz 10 4 -> 10 9 Hz 109-1012Hz
R F s p e c t r o s c o p y i s c o n c e r n e d w i t h t h e i n t e r a c t i o n of m o n o c h r o m a t i c e . m .
w a v e s , R F r a d i a t i o n , with m a t t e r ( a t o m s , m o l e c u l e s , n u c l e i , c o n d e n s e d
m a t t e r ) . We o b s e r v e s p e c t r a l t r a n s i t i o n s b e t w e e n q u a n t u m s t a t e s g o v e r n e d
by t h e B o h r r e l a t i o n
hi/0=Ea - E j = Д Е
175
176 KASTLER
We c a l l t h e m r a d i o f r e q u e n c y r e s o n a n c e s . To be in the H e r t z i a n r a n g e they
m u s t c o r r e s p o n d to s m a l l e n e r g y i n t e r v a l s , v < 10 12 Hz o r X> 0.30 m m .
v = 1 T e r a h e r t z = 10 12 Hz
is e q u i v a l e n t t o A E = 4.2 X 10 eV. T h e p r i n c i p a l s p e c t r a l t r a n s i t i o n s studied

a r e p u r e r o t a t i o n a l l i n e s of m o l e c u l e s in t h e m m and cm w a v e l e n g t h r e g i o n s ,
e l e c t r o n i c p a r a m a g n e t i c r e s o n a n c e ( E P R ) f o r the r e g i o n s
X = 10 c m v = 3 GHz
and X = 3 cm v = 10 GHz
n u c l e a r m a g n e t i c r e s o n a n c e (NMR) f o r
1 to 100 MHz (X= 300 m to 3 m )
T h e t r a n s i t i o n s s t u d i e d in a t o m s c o r r e s p o n d to Z e e m a n i n t e r v a l s a r t i f i c i a l l y
p r o d u c e d by applied m a g n e t i c f i e l d s ( m a g n e t i c r e s o n a n c e t r a n s i t i o n s ) o r to
n a t u r a l f i n e s t r u c t u r e and h y p e r f i n e s t r u c t u r e (HFS) i n t e r v a l s . T h e " n o r m a l "
Z e e m a n s p l i t t i n g is 1.4 MHz in a field of 1 g a u s s , which c o r r e s p o n d s to
2.8 GHz in a field of 2000 g a u s s .
2. S P E C I A L F E A T U R E S O F R F TRANSITIONS
2.1. P r e d o m i n a n c e of induced e m i s s i o n
E i n s t e i n d i s t i n g u i s h e s two e m i s s i o n p r o c e s s e s : s p o n t a n e o u s e m i s s i o n and
induced e m i s s i o n . T h e r a t e is given by
Bp
" c3" 1 ^
A is the r a t e of s p o n t a n e o u s e m i s s i o n and Bp„ is the r a t e of e m i s s i o n induced

by the s p e c t r a l r a d i a t i o n d e n s i t y pv~ dp/dv. In the o p t i c a l r a n g e , pv and X a r e s m a l l ,
and t h e d o m i n a n t p r o c e s s — except in l a s e r s — is s p o n t a n e o u s e m i s s i o n ,
which d e t e r m i n e s the l i f e t i m e of excited s t a t e s of a t o m s .
In the R F r a n g e , X is l a r g e and we a r e able to g e n e r a t e H e r t z i a n
w a v e s of l a r g e pv. The d o m i n a n t p r o c e s s i s induced e m i s s i o n . Spontaneous
e m i s s i o n is n e g l i g i b l e , e x c e p t in a s t r o p h y s i c s .
A c o n s e q u e n c e of t h i s i s that we c a n s o l v e m o s t p r o b l e m s of i n t e r a c t i o n
of r a d i a t i o n and m a t t e r by c l a s s i c a l c a l c u l a t i o n s . It can b e shown t h a t , if
s p o n t a n e o u s e m i s s i o n c a n b e n e g l e c t e d , the e x p e c t a t i o n v a l u e s f o r m a c r o -
s c o p i c q u a n t i t i e s c a l c u l a t e d by quantum m e c h a n i c s a r e i d e n t i c a l with t h e
r e s u l t s of c l a s s i c a l t h e o r y . An e x a m p l e of s u c h a c l a s s i c a l t r e a t m e n t is the
t h e o r y of m a g n e t i c r e s o n a n c e of spins in c o n d e n s e d m a t t e r l e a d i n g to the
" B l o c h e q u a t i o n s " . Induced e m i s s i o n i s the e q u i v a l e n t of n e g a t i v e a b s o r p t i o n .
T h e n e t e f f e c t d e p e n d s on the population d i f f e r e n c e b e t w e e n the l o w e r and
u p p e r e n e r g y l e v e l s of the t r a n s i t i o n .
IAEA - S M R - 1 2 / 9 177
2.2. E l e c t r i c dipóle and m a g n e t i c dipole t r a n s i t i o n s
A n o t h e r s p e c i a l f e a t u r e of R F t r a n s i t i o n s is that in t h e R F r a n g e we
have to d e a l with m a n y t r a n s i t i o n s of the type of m a g n e t i c dipole t r a n s i t i o n s ,
w h e r e a s in t h e o p t i c a l r a n g e t h i s type is s e l d o m found and the c o r r e s p o n d i n g
t r a n s i t i o n s a r e v e r y weak. M o s t of the s p e c t r a l t r a n s i t i o n s o b s e r v e d in the
o p t i c a l r a n g e a r e e l e c t r i c dipole t r a n s i t i o n s and c o r r e s p o n d to the r a d i a t i o n
of an e l e c t r i c dipole.
T h i s e l e c t r i c dipole b e t w e e n two s t a t e s Ej and E ; is given by the
e x p r e s s i o n (its x - c o m p o n e n t )
R, , = e Ф, x d x d y d z , w h e r e Ú is the w a v e - f u n c t i o n of s t a t e E,
J J ' J J
The y - and z - c o m p o n e n t s a r e given by analogous e q u a t i o n s . T h i s c a l c u l a t i o n

l e a d s to the s e l e c t i o n r u l e s and p o l a r i z a t i o n r u l e s . T r a n s i t i o n s b e t w e e n
l e v e l s of the s a m e p a r i t y a r e f o r b i d d e n as e l e c t r i c dipole t r a n s i t i o n s .
Once Pjj is known, we obtain the E i n s t e i n c o e f f i c i e n t s by
B
B - i î i2 P 2 - A - ^ - ^ - P 2
" 3 h j* ' 3h C3
E l e c t r i c dipole t r a n s i t i o n s in the R F region a r e the r o t a t i o n a l l i n e s of m o l e -

c u l e s p o s s e s s i n g a p e r m a n e n t dipole and t h e i n v e r s i o n line of NH 3 . M a g n e t i c
dipole t r a n s i t i o n s obey o t h e r s e l e c t i o n r u l e s and o c c u r b e t w e e n l e v e l s of the
s a m e p a r i t y . T h e y a r e r e l a t e d to the change in m a g n i t u d e or in s p a c e d i r e c -
tion of the m a g n e t i c m o m e n t ß of the atom, and o c c u r in m a g n e t i c r e s o n a n c e s
and in f i n e s t r u c t u r e and HFS r e s o n a n c e s .
2.3. T h e width and s h a p e of r a d i o f r e q u e n c y l i n e s
In t h e o p t i c a l r a n g e the width of n a r r o w s p e c t r a l l i n e s of c o n v e n t i o n a l
light s o u r c e s (gas d i s c h a r g e s ) is d e t e r m i n e d by t h e D o p p l e r e f f e c t .
T h e i n t e n s i t y d i s t r i b u t i o n in an e m i s s i o n o r a b s o r p t i o n line is given by
I.. = I,О EX log 2

P • ' i ?
F o r v-v0 ± 5 / 2 , we have Iv = I0/2. T h e Doppler s h a p e is a G a u s s i a n s h a p e

and б is the width at half i n t e n s i t y . In Fig. 1 6/v0= 0.78 X 1 0 " 6 ^ T / M is given a s
a f u n c t i o n of a b s o l u t e t e m p e r a t u r e and m o l e c u l a r m a s s of the g a s m o l e c u l e s .
T h e r e l a t i v e Doppler width is the s a m e f o r a l l s p e c t r a l l i n e s e m i t t e d o r
a b s o r b e d by t h e s a m e a t o m s o r m o l e c u l e s . In t h e o p t i c a l r a n g e (У 0 ~1О 15 HZ)
it is of the o r d e r б = 10 9 Hz o r 1 GHz. F o r s m a l l R F f r e q u e n c i e s the D o p p l e r
width b e c o m e s v e r y s m a l l and often n e g l i g i b l e , c o m p a r e d with o t h e r b r o a d e n i n g
e f f e c t s . F o r R F l i n e s the line width is m o s t l y d e t e r m i n e d e i t h e r by the
" n a t u r a l line width" o r by r e l a x a t i o n . The n a t u r a l line width c o m e s f r o m t h e
f a c t that the t i m e of i n t e r a c t i o n b e t w e e n the a t o m and the e . m . wave i s
l i m i t e d .to t i m e т a s shown in F i g . 2.
178 KASTLER
FIG.l. Shape of RF line (Gaussian), frequency versus intensity.
A t r u n c a t e d m o n o c h r o m a t i c s i n u s o i d a l wave is — a s shown by F o u r i e r
a n a l y s i s — t h e e q u i v a l e n t of the s u p e r p o s i t i o n of w a v e s of a f r e q u e n c y
interval
1 2LR
sOU) = T- or * V =
Б
T
which l e a d s to ô E = ftôw =ÍIT" 1 o r 6Ет =fi. T h i s is H e i s e n b e r g ' s f o u r t h

u n c e r t a i n t y r e l a t i o n . T h e f i n i t e l i f e t i m e of an e n e r g y l e v e l т l e a d s to a
s p r e a d i n g of the e n e r g y of t h i s level. A s p e c t r a l line i s a t r a n s i t i o n b e t w e e n
two l e v e l s , E j and E 2 , v = l / h ( E j - E 2 ) and t h e c o r r e s p o n d i n g u n c e r t a i n t y i s
1 1" i
ôv= i(6E1 + ÔE 2 )= ± — + —
LVstJ 2тг - T 1 T
2-
If t h e two l i f e t i m e s a r e e q u a l ( Z e e m a n l e v e l s )
6v = - i -
7ГТ
M o r e g e n e r a l l y , we will c a l l т the " c o h e r e n c e t i m e " . T h i s i s the f o r m u l a

f o r the n a t u r a l line width of m a g n e t i c r e s o n a n c e in an e x c i t e d s t a t e . F o r a
g r o u n d - s t a t e r e s o n a n c e , т is t o b e i d e n t i f i e d with the " t r a n s v e r s e r e l a x a t i o n
IAEA - S M R - 1 2 / 9 179
t i m e " T 2 : 6 v = 1 /7гТ2 . T h e s h a p e c o n n e c t e d to t h i s n a t u r a l width is a

Lorentz shape,
I=
w h e r e 6' = öv.
B r o a d e n i n g o c c u r s a l s o by r a d i o f r e q u e n c y p o w e r and by c o l l i s i o n s
(pressure broadening).
3. SHORT HISTORICAL SURVEY
T h e f i r s t R F t r a n s i t i o n o b s e r v e d (1934) was the i n v e r s i o n band of NH 3

in t h e 1 . 2 5 - c m w a v e l e n g t h r a n g e , w h e r e it was d i s c o v e r e d by C l e e t o n and
W i l l i a m s . It w a s e x p e c t e d f r o m t h e a n a l y s i s of the i n f r a - r e d r o t a t i o n l i n e s
of t h e s e m o l e c u l e s in 1933. E a c h of t h e s e l i n e s i s a doublet as p r e d i c t e d by
D e n n i s on.
In 1938 Rabi (Columbia U n i v e r s i t y ) s t a r t e d h i s m o l e c u l a r b e a m m e t h o d
of m a g n e t i c r e s o n a n c e . But the l a r g e - s c a l e d e v e l o p m e n t of R F s p e c t r o s c o p y
s t a r t e d in 1944-45 with the invention of e l e c t r o n i c d e t e c t i o n t e c h n i q u e s :
(1) T h e a p p l i c a t i o n of r a d a r t e c h n i q u e s to the study of m o l e c u l a r t r a n s i t i o n s

in the m i c r o w a v e r e g i o n .
(2) T h e d i s c o v e r y of E P R ( E l e c t r o n P a r a m a g n e t i c R e s o n a n c e ) by Z a v o i s k y
in K a z a n .
(3) T h e d i s c o v e r y of NMR ( N u c l e a r M a g n e t i c R e s o n a n c e ) s i m u l t a n e o u s l y ,
by P u r c e l l , T o r r e y and Pound at H a r v a r d , and by F e l i x B l o c h and his
c o l l a b o r a t o r s in S t a n f o r d .
4. PRODUCTION AND D E T E C T I O N OF R F TRANSITIONS
4.1. Production
T r a n s i t i o n s a r e p r o d u c e d by i n t e r a c t i o n of a t o m s o r m o l e c u l e s with a
m o n o c h r o m a t i c e. m . wave p r o d u c e d by a g e n e r a t o r . R F g e n e r a t o r s have
b e e n d e v e l o p e d f o r the p u r p o s e s of r a d i o c o m m u n i c a t i o n s (1 to 100 MHz), of
t e l e v i s i o n (100 MHz - 1 GHz), and r a d a r (3 to 10 GHz). In the R F r e g i o n
L - C c i r c u i t s a r e u s e d ; in t h e m i c r o w a v e r e g i o n wave guide t e c h n i q u e s and
r e s o n a n c e c a v i t i e s h a v e b e e n d e v e l o p e d . T h e m a t t e r u n d e r i n v e s t i g a t i o n is
s u b m i t t e d e i t h e r t o a p r o g r e s s i v e e . m . wave o r to a s t a n d i n g wave ( c o n d e n s e r +
s e l f - i n d u c t i o n c o i l , r e s o n a n c e cavity).
4.2. Detection
The m e t h o d s of d e t e c t i o n c a n b e divided into two c l a s s e s . D u r i n g t h e

i n t e r a c t i o n b e t w e e n m a t t e r and r a d i a t i o n at r e s o n a n c e , both t h e p r o p e r t i e s
of the m a t t e r and t h e p r o p e r t i e s of the r a d i a t i o n a r e m o d i f i e d . In one c l a s s
180 KASTLER
F (
21 A • V2
~ T -v2
FIG.3. Schematic representation of Rabi 1 s molecular-beam device.
of d e t e c t i o n m e t h o d s one o b s e r v e s the change p r o d u c e d on the wave or on the

R F c i r c u i t g e n e r a t i n g the w a v e . T h e s e m e t h o d s of d e t e c t i o n a r e c a l l e d
e l e c t r o n i c d e t e c t i o n m e t h o d s . In the o t h e r c l a s s , one o b s e r v e s the c h a n g e
p r o d u c e d on t h e a t o m s o r m o l e c u l e s . We d e a l f i r s t with t h e l a t t e r m e t h o d s .
4.3. Rabi's detection method using molecular beams
M o l e c u l a r b e a m s in v a c u u m w e r e p r o d u c e d f i r s t by L o u i s D u n o y e r in
1911. T h e y w e r e u s e d by S t e r n to e s t a b l i s h the M a x w e l l d i s t r i b u t i o n law of
t h e r m a l v e l o c i t i e s and, in 1922, in the S t e r n - G e r l a c h e x p e r i m e n t , giving
the e x p e r i m e n t a l proof of s p a c e q u a n t i z a t i o n of a t o m s in a m a g n e t i c f i e l d .
F i g . 3 s h o w s t h e s c h e m e of R a b i ' s d e v i c e .
Atoms e s c a p e f r o m a h e a t e d oven o r a g a s c h a m b e r О t h r o u g h a s m a l l s l i t Fj
into a v a c u u m . T h e a p e r t u r e of the b e a m is l i m i t e d by a s e c o n d l a r g e r s l i t ,
F 2 , allowing an a n g u l a r a p e r t u r e of 2 a . A and В a r e t h e g a p s of two m a g n e t s
p r o d u c i n g n o n - h o m o g e n e o u s m a g n e t i c f i e l d s of the s a m e d i r e c t i o n , p e r p e n d i -
c u l a r to t h e m e a n r a y of t h e b e a m , but of opposite g r a d i e n t s . T h e f o r c e
e x e r t e d on a p a r a m a g n e t i c a t o m is F z = J u z (3H/3z) w h e r e /J z is the z - c o m p o n e n t
of the m o m e n t . It p r o d u c e s a c u r v a t u r e of the a t o m i c p a t h , c u r v a t u r e of
o p p o s i t e d i r e c t i o n in the A and В f i e l d s . A s l i t S b e t w e e n the two gaps s e l e c t s
a t o m s which a r e f o c u s s e d on a d e t e c t o r D, counting the a t o m s a r r i v i n g on it.
If now, in the S - r e g i o n , a m a g n e t i c r e s o n a n c e t r a n s i t i o n is p r o d u c e d by an
R F f i e l d , t r a n s i t i o n s o c c u r and, as a r e s u l t , the path of a t o m s h a v i n g u n d e r -
gone t r a n s i t i o n s i s changed in the gap B, and t h e s e a t o m s do not r e a c h the
d e t e c t o r . M a g n e t i c r e s o n a n c e is m o n i t o r e d by a d e c r e a s e in the s i g n a l at D.
F i g u r e 20 s h o w s an NMR s i g n a l of 7 L i in L i C l m o l e c u l e s . The R F f r e q u e n c y
applied is v = 3.518 MHz and the m a g n e t i c f i e l d HQ is swept t h r o u g h r e s o n a n c e
which o c c u r s at 2134 G a u s s . In this c a s e the r e s o n a n c e f r e q u e n c y v0 is a
2 w e = to0 = yH 0 and 7 = Hj/ift
/Uj can b e c a l c u l a t e d and e x p r e s s e d in juN u n i t s :
UM = ; r ! i r - = = 5.049 X Ю" 24 e r g6 // gs a u s s
2MH 1840
[MB = B o h r ' s m a g n e t o n ] .
IAEA - S M R - 1 2 / 9 181
63P, - о
--1
TX CT 2537Â
e'Sn-L • 0 GROUND STATE
FIG.4. Excited state of the Hg a t o m (excitation by тг-polarized light at 2537 A)-
i 6 8 10 12 U 16
GAUSS
FIG.5. EPR absorption detected by m e c h a n i c a l torque on the substance DPPH (after G. Alzetta and A. Gozzini,
Proc. 12-th C o l l . AmpĚre, Bordeaux 1963. North Holland Publ. (1964) 209.)
4.4. T h e o p t i c a l d e t e c t i o n m e t h o d of R F r e s o n a n c e s
T h i s m e t h o d i s s u i t a b l e f o r s t u d y i n g r e s o n a n c e s in e x c i t e d s t a t e s of
a t o m s . It i s p o s s i b l e , e i t h e r by o p t i c a l e x c i t a t i o n ( s p a c e - d i r e c t e d and
p o l a r i z e d l i g h t ) o r by e l e c t r o n - i m p a c t e x c i t a t i o n w i t h a u n i d i r e c t i o n a l e l e c t r o n
b e a m , t o a c h i e v e s e l e c t i v e p o p u l a t i o n of Z e e m a n l e v e l s of the e x c i t e d s t a t e .
T h i s g i v e s r i s e to p o l a r i z a t i o n of t h e o p t i c a l l i n e s e m i t t e d and t o s p a c e -
a n i s o t r o p y of the l i g h t e m i s s i o n . By R F r e s o n a n c e b e t w e e n Z e e m a n l e v e l s
o r H F S l e v e l s of the e x c i t e d s t a t e , t h e light e m i t t e d i s d e p o l a r i z e d and t h e
r e s o n a n c e c a n be d e t e c t e d in t h i s w a y .
E x a m p l e : B r o s s e l ' s d o u b l e r e s o n a n c e e x p e r i m e n t on t h e e x c i t e d s t a t e of
t h e Hg a t o m ( F i g . 4). H g - v a p o u r i s e x c i t e d b y т т - p o l a r i z e d l i g h t of 2537 A.
M a g n e t i c r e s o n a n c e g i v e s r i s e to t h e e m i s s i o n of a - l i g h t w h o s e i n t e n s i t y I a
c a n b e m e a s u r e d a s a f u n c t i o n of t h e f i e l d H 0 . F o r v = 144 M H z , r e s o n a n c e
o c c u r s at 69 g a u s s . W e h a v e t o d e a l h e r e with a t r i g g e r d e t e c t i o n .
182 KASTLER
A t o m i c " o r i e n t a t i o n " and " a l i g n m e n t " . Atomic orientation or polarization

is d e f i n e d by the d e g r e e of o r i e n t a t i o n
+J
XmNir
J +J
I».
-J
In this f o r m u l a , J is the i n t e r n a l quantum n u m b e r , m the m a g n e t i c quantum

n u m b e r and N m the population of a Z e e m a n s u b - l e v e l . O r i e n t a t i o n c a n be
obtained by o p t i c a l e x c i t a t i o n with c i r c u l a r l y p o l a r i z e d light. Such light
c a r r i e s a n g u l a r m o m e n t u m which, by the a b s o r p t i o n p r o c e s s , is t r a n s f e r r e d
to the a t o m s . E x c i t a t i o n with s p a c e - d i r e c t e d n a t u r a l light, o r with l i n e a r l y -
p o l a r i z e d light, o r with e l e c t r o n i m p a c t l e a d s to " a l i g n m e n t " , which is
e q u i v a l e n t to " a n i s o t r o p y " . T h e d e g r e e of a l i g n m e n t is d e f i n e d by
+J
/ т 2 \ J ( J + 1> -I J ( J + 1)
^ z/ " 3
I N„
O r i e n t a t i o n or a l i g n m e n t can be t r a n s f e r r e d to the g r o u n d s t a t e of a t o m s by
the optical pumping technique.
O r i e n t a t i o n p r o d u c e s a m a c r o s c o p i c a n g u l a r m o m e n t u m in a v a p o u r
= NPJh
IAEA - S M R - 1 2 / 9 183
- ж -
I ^TO
AMPLIFIER
hrw^
SIGNAL
GENERATOR
4- CABLE
II
/77777 ПЯЛЛР
FIG.7. Purcell's balanced bridge technique.
and an a s s o c i a t e d m a c r o s c o p i c m a g n e t i c m o m e n t
NPm = N P g J n B
At t h e r m a l e q u i l i b r i u m in a m a g n e t i c f i e l d
E„\ ( pHX
N m = c o n s t X exp p j - J = К exp m J k T .
T h i s l e a d s , if E m « kT, to P = ( p H / J k T ) ( E m 2 / 2 J + 1 ) and, a s
+J
IJ
m =
J( J + 1 )(2 J- i )
We d e f i n e x0 = •stí?/H a s p a r a m a g n e t i c s u s c e p t i b i l i t y .
4.5. M a g n e t i c r e s o n a n c e d e t e c t e d by the t r a n s f e r of a n g u l a r m o m e n t u m
We s h a l l s e e l a t e r on that if we apply, to a p a r a m a g n e t i c s u b s t a n c e in
c o n d e n s e d s t a t e at e x a c t r e s o n a n c e , an R F f i e l d 2 H 1 c o s u 0 t , the p o w e r
t r a n s m i t t e d to the s u b s t a n c e in unit t i m e is given by
H 21 T
W = x —-—
0 0 2 2
1 + y HT T
1 1 2
184 KASTLER
w h e r e Tj and T 2 a r e , r e s p e c t i v e l y , t h e l o n g i t u d i n a l and t r a n s v e r s e
r e l a x a t i o n t i m e s . T h e s a t u r a t i o n f a c t o r is d e f i n e d as
2
1 + 7 H 2 T i T2
T h i s p o w e r i s c o n v e r t e d into h e a t and, in p r i n c i p l e , the heat p r o d u c t i o n

could be u s e d f o r the d e t e c t i o n of r e s o n a n c e . T h i s would be a " c a l o r i m e t r i c
method".
In 1936, G o r t e r , at L e i d e n , t r i e d to d e t e c t NMR by this m e t h o d . He
f a i l e d and c o r r e c t l y a t t r i b u t e d this n e g a t i v e r e s u l t to a v e r y long T j r e l a x a t i o n
t i m e ; s o the s a t u r a t i o n f a c t o r s and the h e a t g e n e r a t e d a r e v e r y s m a l l in
this case.
F o r e a c h a b s o r b e d R F photon of e n e r g y ftu>0, an a n g u l a r m o m e n t u m h
i s t r a n s f e r r e d to t h e s a m p l e . This a n g u l a r m o m e n t u m t r a n s f e r ( d P / d t )
p r o d u c e s a t o r q u e Г on the s a m p l e :
_ dP W TT2 ^
= =
dT ~ *oVoT2 s
T h i s t o r q u e h a s b e e n m e a s u r e d by Gozzini on the D P P H m a g n e t i c r e s o n a n c e
(Fig. 5).
4.6. D e t e c t i o n of m a g n e t i c r e s o n a n c e by n u c l e a r p h y s i c s t e c h n i q u e s
A n o t h e r m e t h o d of d e t e c t i o n of R F r e s o n a n c e s is to m o n i t o r the change
of population of m s t a t e s by the change in e m i s s i o n r a t e of n u c l e a r p a r t i c l e s
in d i f f e r e n t d i r e c t i o n s of s p a c e . We s h a l l s e e two e x a m p l e s of this when we
s h a l l r e p o r t on t h e s t u d i e s of m a g n e t i c r e s o n a n c e in p o s i t r o n i u m and in
muonium.
4.7. T h e e l e c t r o n i c d e t e c t i o n m e t h o d s of R F r e s o n a n c e s
T h e s e m e t h o d s a r e b a s e d on the f a c t that the i n t e r a c t i o n b e t w e e n the

e. m . wave and m a t t e r , which c o n s i s t s in an e x c h a n g e of e n e r g y , c h a n g e s
t h e p r o p e r t i e s of the wave and c h a n g e s a l s o the p r o p e r t i e s of the R F c i r c u i t
p r o d u c i n g the wave. An a b s o r p t i o n of e. m . e n e r g y by m a t t e r is e q u i v a l e n t
to a l o s s of e n e r g y of t h e c i r c u i t and c o r r e s p o n d s to an i n c r e a s e of i t s
resistance.
To an a b s o r p t i o n band in t h e f r e q u e n c y s c a l e is c o n n e c t e d .a c u r v e of
a n o m a l o u s d i s p e r s i o n , shown in Fig. 6.
T h e d i s p e r s i o n e f f e c t c o r r e s p o n d s t o a c h a n g e in the c a p a c i t y С o r in the
s e l f - i n d u c t i o n c o e f f i c i e n t L of the RF c i r c u i t . T h e s e c h a n g e s can b e d e t e c t e d
by v e r y s e n s i t i v e e l e c t r o n i c m e t h o d s , e . g . with the help of P u r c e l l ' s
b a l a n c e d b r i d g e t e c h n i q u e (Fig. 7).
T h e two s i g n a l s a r r i v i n g at В a r e of e q u a l a m p l i t u d e , but opposite in
p h a s e and give r i s e to d e s t r u c t i v e i n t e r f e r e n c e . A d i s t u r b a n c e in one of the
c i r c u i t s , p r o d u c e d by the r e s o n a n c e , c h a n g e s the b r i d g e e q u i l i b r i u m and
g i v e s r i s e to a s i g n a l . T h e s a m p l e s t u d i e d is p l a c e d i n s i d e the induction
IAEA - S M R - 1 2 / 9 185
c o i l of one of the two c i r c u i t s in t h e gap of an e l e c t r o m a g n e t (Fig. 8).

A n o t h e r p o s s i b i l i t y is F e l i x B l o c h ' s m e t h o d of " n u c l e a r induction"
(Fig. 9). It u s e s two i n d e p e n d e n t L - C c i r c u i t s with o r t h o g o n a l c o i l s , t h e i r
m u t u a l induction c o e f f i c i e n t M b e i n g z e r o . T h e i n t r o d u c t i o n of m a t t e r in the
c o m m o n p a r t s of the two c o i l s L-l and L 2 , and the a p p l i c a t i o n of a s t e a d y f i e l d H 0 ,
p e r p e n d i c u l a r to t h e s h e e t and to t h e two coil a x e s , p r o d u c e s a n o n - z e r o
induction e f f e c t when r e s o n a n c e i s r e a l i z e d . T h i s m e t h o d is b a s e d on the
f a c t that the m a g n e t i c m o m e n t induced in the m a t t e r by the l i n e a r R F f i e l d
2Щ c o s u t is a r o t a t i n g m o m e n t in the p l a n e p e r p e n d i c u l a r to HQ.
5. THE BEHAVIOUR O F PARAMAGNETIC ATOMIC S T A T E S IN A

CONSTANT F I E L D AND IN A RADIOFREQU-ENCY F I E L D
5.1. Definitions
We c a l l " p a r a m a g n e t i c " an a t o m i c s t a t e p o s s e s s i n g an a n g u l a r m o m e n t u m
p and a m a g n e t i c m o m e n t ju which a r e c o - a x i a l . We w r i t e ju = 7p, which
d e f i n e s 7, c a l l e d " g y r o m a g n e t i c r a t i o " .
i 1 l e
F o r a f r e e e l e c t r o n | p| = — h and,u = ц в = — — h
186 KASTLER
T h e two a x i a l v e c t o r s , p and ^ a r e in o p p o s i t e d i r e c t i o n s .
For an e l e c t r o n o r b i t р { = ih and = i-/u B w h e r e i is the a z i m u t h a l
quantum number.
For an o r b i t t h e g y r o m a g n e t i c r a t i o is
7c = =
2m 0 " 2m,
F o r the electron spin % = e / m 0 = - | e | / m 0 . The Lande factor g is

d e f i n e d b y I 7 I = g ( e / 2 m 0 ) . F o r o r b i t s , g = l ; f o r e l e c t r o n s p i n s , g = 2.
M o r e g e n e r a l l y , f o r an a t o m i c s t a t e , J = E + § d e f i n e s the t o t a l a n g u l a r
m o m e n t u m Jft. T h e m a g n e t i c m o m e n t a s s o c i a t e d with it is p j = - g j J/uB ,
w h e r e gj is g i v e n by L a n d é ' s f o r m u l a
J ( J + 1 ) + S (S + 1) - L ( L + 1 )
g
J 2J(J+1 )
L = EJ2 b e i n g the r e s u l t a n t of the o r b i t a l m o m e n t s of a l l e l e c t r o n s , and S = E s

t h e r e s u l t a n t of t h e i r s p i n m o m e n t s . F o r s i n g l e t t e r m s the r e s u l t a n t of
e l e c t r o n s p i n s i s S = 0. We h a v e J = L and g= 1. F o r p u r e s p i n s t a t e s
( S - s t a t e s ) we h a v e L = 0 and J = S, g= 2. T h i s is in p a r t i c u l a r the c a s e of the
g r o u n d s t a t e s of t h e H - a t o m and of t h e a l k a l i a t o m s which a r e in a s t a t e
2
S I : L = 0, J = S = 1 / 2 .
5.2. B e h a v i o u r of an a t o m i c s y s t e m in a c o n s t a n t m a g n e t i c field
The L a r m o r p r e c e s s i o n . L e t u s t a k e H0 in the z - d i r e c t i o n of a fixed

c o - o r d i n a t e s y s t e m and c a l l t h e x y - p l a n e the " e q u a t o r i a l p l a n e " . T h e f i e l d
H0 e x e r t s on a m a g n e t i c m o m e n t a t o r q u e
b i x i i ,
A c c o r d i n g to a t h e o r e m of m e c h a n i c s , Г = ( d p / d t ) ; p = ( l / y ) ß g i v e s
(1 /7)(dju/dt) = (i X H 0 ; dß = у ц X H Q d t i s a v e c t o r p e r p e n d i c u l a r to t h e p l a n e
П, Й (Fig. 10).
[Г I = ju H 0 s i n a and |clju| = ß s i n e dö if d6 is the a n g u l a r p r e c e s s i o n of
ц in t i m e dt a r o u n d H 0 : &ÍH-S d0 = y # HQ ßin-a dt.
u 0 = ( d 0 / d t ) = 7 H 0 i s t h e a n g u l a r s p e e d o r the c i r c u l a r f r e q u e n c y of the
" L a r m o r p r e c e s s i o n " of ц and p a r o u n d H 0 ,
The s e n s e of t h i s p r e c e s s i o n can be s e e n f r o m t h e f r a m e in F i g . 11.
We r e t a i n the r u l e that f o r an . e l e c t r o n the s e n s e of p r e c e s s i o n is t h a t of
t h e e l e c t r i c c u r r e n t in the c o i l c r e a t i n g the f i e l d H 0 . If we d e f i n e t h i s s e n s e
a s the p o s i t i v e s e n s e , we have f o r e l e c t r o n s u 0 > 0, but y< 0, s o we h a v e to
w r i t e u 0 = - 7 HQ.
IAEA - S M R - 1 2 / 9 187
The r o t a t i n g f r a m e . We i n t r o d u c e a r o t a t i n g f r a m e OXYZ h a v i n g Z = z ,
which r o t a t e s a r o u n d the z - a x i s with a n g u l a r v e l o c i t y 10 ( F i g . 12). F o r an
o b s e r v e r in t h e r o t a t i n g f r a m e , the a n g u l a r v e l o c i t y of the L a r m o r p r e c e s s i o n
s e e n by h i m i s r e d u c e d to w0 -to. He c o n c l u d e s t h a t the m a g n e t i c f i e l d he
s e e s in the z - d i r e c t i o n i s
<y U <y <Y
If и = u 0 t h e m a g n e t i c f i e l d v a n i s h e s f o r h i m . But n o t e t h a t t h i s c o n c l u s i o n
h a s n o a b s o l u t e m e a n i n g . It d e p e n d s on the 7 - v a l u e of the s t a t e c o n s i d e r e d .
5.3. B e h a v i o u r of a c o l l e c t i o n of m a n y p a r a m a g n e t i c a t o m s in a m a g n e t i c
f i e l d Hn
E a c h a t o m h a s a m o m e n t jÜ, but the m o m e n t s m a y h a v e d i f f e r e n t

o r i e n t a t i o n s in s p a c e . T h e bulk m a c r o s c o p i c m o m e n t i s M = ЕД. If n o f i e l d
is p r e s e n t , M = 0, which c o r r e s p o n d s to r a n d o m s p a c e o r i e n t a t i o n .
188 KASTLER
FIG.13. Precession of atomic magnetic moment.
FIG. 14. Frame used in classical phenomenological theory.
In A f i e l d H 0 || OZ we have M = М г f o r s y m m e t r y r e a s o n s . At t h e r m a l
e q u i l i b r i u m , 'M z = ХоЩ. T h i s d e f i n e s the p a r a m a g n e t i c s u s c e p t i b i l i t y
J+1
у = T4T
N ß—2
3J kT
It e x p r e s s e s C u r i e ' s law. M z i s called the " l o n g i t u d i n a l m a g n e t i c m o m e n t " .

T h e m a g n e t i c m o m e n t of e a c h a t o m h a s a l s o a t r a n s v e r s e c o m p o n e n t which
p r e c e s s e s a r o u n d H 0 with t h e L a r m o r s p e e d u 0 = 7H 0 (Fig. 13). But if the
only a c t i o n on the a t o m i c m o m e n t s is that of a c o n s t a n t f i e l d HQ. the r e s u l t a n t
M t = E/I t is in g e n e r a l v a n i s h i n g f o r s y m m e t r y r e a s o n s . T h e p h a s e s of
p r e c e s s i o n of the a t o m s a r e d i s t r i b u t e d at r a n d o m . We s a y the a t o m s
precess "incoherently". T h e r e exist p r o c e d u r e s for c r e a t i n g a coherence
of p h a s e a m o n g the p r e c e s s i n g a t o m s . In this c a s e ïvlt = E/Üt is d i f f e r e n t f r o m
z e r o . T h e m a c r o s c o p i c m o m e n t M t p r e c e s s e s with the L a r m o r s p e e d u 0 = -7H 0
a r o u n d H 0 . We s p e a k of a " c o h e r e n t " p r e c e s s i o n . If the c a u s e of c o h e r e n c e
is s u d d e n l y s u p p r e s s e d , t h e individual m o m e n t s l o s e t h e i r c o h e r e n c e and the
t r a n s v e r s e m o m e n t M t d e c l i n e s a s an e x p o n e n t i a l f u n c t i o n of t i m e and
dMt_ Mj
"ďt T„
IAEA - S M R - 1 2 / 9 189
2H,
FIG.15. Field rotation (amplitude 21-Ij) in coherence with w .
d e f i n e s a " t r a n s v e r s e r e l a x a t i o n t i m e T 2 " , often called s p i n - s p i n r e l a x a t i o n

time.
If the l o n g i t u d i n a l m o m e n t M z i s suddenly d i s t u r b e d (for e x a m p l e , by a
sudden c h a n g e of t h e f i e l d v a l u e H 0 ) it r e t u r n s to its e q u i l i b r i u m v a l u e
e x p o n e n t i a l l y , a c c o r d i n g to a d i f f e r e n t i a l equation of t h e f o r m
dM,"Z _ M z (t) - Mo
~dt
T j is c a l l e d the " l o n g i t u d i n a l r e l a x a t i o n t i m e " o r the " s p i n - l a t t i c e r e l a x a t i o n

t i m e " . In g e n e r a l T 2 š T x .
5.4. B e h a v i o u r of a c o l l e c t i o n of a t o m s in an R F field
If a r a d i o f r e q u e n c y field is i n t r o d u c e d , it p r o d u c e s , at r e s o n a n c e ,
t r a n s i t i o n s b e t w e e n q u a n t u m s t a t e s of a t o m s . T h e s e m a g n e t i c dipole
t r a n s i t i o n s a r e s t u d i e d in q u a n t u m m e c h a n i c s , which e s t a b l i s h e s f o r m u l a s f o r
the t r a n s i t i o n p r o b a b i l i t i e s m m±l.
In t h e R F r e g i o n t h e n u m b e r of photons p r e s e n t is a l w a y s v e r y l a r g e and
s p o n t a n e o u s e m i s s i o n is n e g l i g i b l e . It c a n be shown that in t h i s c a s e 1 t h e
e x p e c t a t i o n v a l u e s obtained f o r m a c r o s c o p i c q u a n t i t i e s •\MZ)> and ^ M ^ a r e
i d e n t i c a l to t h e v a l u e s c a l c u l a t e d by a s s u m i n g a c l a s s i c a l b e h a v i o u r of t h e s e
quantities.
We s h a l l d e v e l o p a c l a s s i c a l p h e n o m e n o l o g i c a l t h e o r y (Fig. 14):
A c o l l e c t i o n of p a r a m a g n e t i c a t o m s (or ions o r nuclei) p l a c e d in a c o n s t a n t
f i e l d H 0 || Oz, p o s s e s s e s a l o n g i t u d i n a l m a g n e t i c m o m e n t Й 2 = M 0 = X q H q . At
t i m e t= 0 we i n t r o d u c e an R F f i e l d H x = 2HX c o s u t p a r a l l e l to the x - a x i s . What
will h a p p e n ? T h e r e c t i l i n e a r o s c i l l a t i n g field of a m p l i t u d e 2H;! c a n b e c o n -
s i d e r e d as a c o h e r e n t s u p e r p o s i t i o n of two r o t a t i n g f i e l d s , e a c h of a m p l i t u d e
Hj, r o t a t i n g in the e q u a t o r i a l x y - p l a n e in o p p o s i t e d i r e c t i o n s : one c l o c k - w i s e ,
the o t h e r a n t i - c l o c k w i s e . T h e y r o t a t e in p h a s e c o h e r e n c e with a n g u l a r
s p e e d ±io ( F i g . 15). An o b s e r v e r in a f r a m e r o t a t i n g at s p e e d ш (the s a m e
as t h e s p e e d of one of t h e s e f i e l d s ) w i l l s e e t h i s field Hj as a fixed c o n s t a n t
1
A. Abragam, T h e Principles of Nuclear Magnetism, Clarendon Press (1961), chapters II and 1П.
190 KASTLER
f i e l d i n t h e X - d i r e c t i o n of h i s r o t a t i n g f r a m e X Y Z . In t h e Z - d i r e c t i o n he
s e e s the field
to
H' = H n + -
T h e r e s u l t a n t of t h e s e two f i e l d s i s a f i e l d H £ff (H e f f e c t i v e ) in t h e X Z - p l a n e
of m a g n i t u d e
1/2
H eff
m a k i n g , with t h e Z - a x i s , a n a n g l e given by t a n 6 = (Hj/Hq) + u / y ) . F o r t h i s

o b s e r v e r t h i s f i e l d i s a s t e a d y f i e l d and in h i s f r a m e h e w i l l o b s e r v e t h e
L a r m o r p r e c e s s i o n of M a r o u n d H eff w i t h s p e e d и = - 7 H e f f .
At e x a c t r e s o n a n c e (и =ш0) t h e f i e l d c o m p o n e n t in the Z - d i r e c t i o n i s
H 0 + ( u 0 / 7 ) = 0 a s u 0 = ~ 7 H 0 . So, in t h i s c a s e , t h e only f i e l d s e e n by t h e
o b s e r v e r i s Hj|| OX, and f o r h i m t h e L a r m o r p r e c e s s i o n of M t a k e s p l a c e
in t h e Z Y - p l a n e with a n g u l a r s p e e d Uj = - y Hj. T h i s m o t i o n i s c a l l e d the
"nutation motion".
After a time
t - i l l - "
1
"l 21 7 I H 1
t h e l o n g i t u d i n a l m o m e n t M z i s t r a n s f o r m e d into a t r a n s v e r s e m o m e n t M t = My
a l o n g OY. If at t h i s t i m e t j we cut off t h e R F f i e l d , we h a v e p e r f o r m e d a
"90° p u l s e " and M t w i l l , in t h e l a b o r a t o r y f r a m e , m a k e a " f r e e p r e c e s s i o n "
and d e c a y with r e l a x a t i o n t i m e T 2 . But if the R F a c t i o n g o e s on, a f t e r t i m e
t 2 = 2 t 1 ; t h e m o m e n t b e c o m e s a l o n g i t u d i n a l m o m e n t in t h e - Z - d i r e c t i o n . We
h a v e , if we s t o p R F p o w e r at t i m e t 2 , p e r f o r m e d a 180° p u l s e . If we s t o p
t h e R F p o w e r at t h i s t i m e , M z w i l l r e t u r n to i t s e q u i l i b r i u m v a l u e M Q in t h e
f i e l d H 0 with r e l a x a t i o n t i m e T ^ Q u a n t u m m e c h a n i c a l l y a 180° p u l s e c o r r e s -
ponds to a "population i n v e r s i o n " .
5.5. C l a s s i c a l t h e o r y of the m o t i o n of a s p m - s u b m i t t e d t o a c o n s t a n t f i e l d
and an R F f i e l d
L e t u s now c o n s i d e r t h e c a s e of a p e r m a n e n t a p p l i c a t i o n of t h e R F f i e l d and
e s t a b l i s h by c a l c u l a t i o n t h e b e h a v i o u r of Й in a s t e a d y - s t a t e s i t u a t i o n . 2
T h i s w i l l l e a d u s t o t h e B l o c h e q u a t i o n s . We e s t a b l i s h t h e s e e q u a t i o n s in t h e
r o t a t i n g f r a m e X Y Z w h e r e we i n t r o d u c e t h e u n i t v e c t o r s i, j , k a l o n g t h e
a x e s X , Y , Z ( F i g . 16). T h e r e l a x a t i o n r e l a t i o n s a r e
dMx _ Mx dMy _ M^ dMz _ Mz-M0

~dt ' dt " " T2 ' ~dt %
2
We have neglected the effect of the field rotating in the opposite direction ( w « - ш 0 ). It can be shown
that it is negligible if Hj remains small (Hj « H0 ) .
IAEA - S M R - 1 2 / 9 191
We c o m b i n e t h e s e t h r e e r e l a t i o n s in w r i t i n g t h e v e c t o r - r e l a t i o n :
J k + (1)
dt т2 T2 Tl Tl
T h e e f f e c t of t h e f i e l d H e f f on M i s g o v e r n e d by t h e r e l a t i o n :
X H e f f ) = (M X 7 H e f f ) where 7Heff = (w-u 0 )k - W J
w h e r e we h a v e w r i t t e n Uj = - 7 H j . I n t r o d u c i n g Дw = u - ш0 , we o b t a i n
^ = ( M X Ï + M Y J + MZ к ) X ( Д и к - И / )
= -ДшМх]+ДшМуГ + и 1 М у к - и 1 м Д (2)
C o m b i n i n g (1) and (2) we g e t :
dM / Mx f Mv /М0 мг v
_ = ( _ _ * + дш My ) i - (лш M . - J - ^ M j i + (-S - к
We s e a r c h f o r a s t e a d y - s t a t e s o l u t i o n d M / d t = 0, s o i t s t h r e e c o m p o n e n t s
must be all zero:
(a) - М х + Т2ДшМу = 0 >М х = Т 2 Д и М у
(b) Т2 Д ш М Х - М У - WIT2MZ = 0
(c) M0-Mz + TlUlMy = 0 » M2 = M 0 + w 1 T 1 M y

192 KASTLER
I n t r o d u c i n g t h e s e v a l u e s of M and M into (b) we obtain:
M, 1 + Т 2 Д и + T T u2
2 1 2 1 "T2"lM0
T
2"l
M y = - M0
1+T® T 2 uJ
T Дьш
2 i
M - M,О о о о
1 + Т2 Ди + Т 1 Т2 ш1
м „ = м, 1 - Ti T 8 m z
1 + т 2 Дю + Т г Т 2 с
2 2
1 tTgAu)!
M
О о 2 2
1+ т2дш +TlT2Ul
We r e - i n t r o d u c e Ди = и-Ш 0 and И, = -THj. R e m e m b e r that 7 <0, SOCJ 1 >0 )

which p e r m i t s u s to w r i t e = H-l,
TJTI H
M„ = - M.
У 0 92 9 9 9
1+Т2 (и-Шо)2+Т1Т2Т2Н2
T2 Ы Н г Ы о - ц )
M* + м„
1+T ( U -CÜ„) 2 + T 1 T 2 7 2 H 2
2
1 -T 2 2 (u-u 0 ) 2
M = M,
° 1 + T 2 ( i o - U o ) 2 + T 1 T 2 72 H 2
It is c u s t o m a r y to w r i t e - M y = v and M^ = u.
5.6. D i s c u s s i o n of t h e Bloch e q u a t i o n s
We m u s t d i s c u s s t h e s e r e s u l t s . F i r s t n o t e that t h e s e m o m e n t s a r e given
in the r o t a t i n g f r a m e . So t h e t r a n s v e r s e m o m e n t M t =1 M x + jMy is r o t a t i n g
in the l a b o r a t o r y f r a m e and g i v e s r i s e to an induced e l e c t r o m o t i v e f o r c e in a
IAEA - S M R - 1 2 / 9 193
FIG. 17. P l o t of v a n d u as f u n c t i o n s of w.
coil p e r p e n d i c u l a r to the c o i l p r o d u c i n g the o s c i l l a t o r y R F f i e l d . T h i s

j u s t i f i e s B l o c h ' s d e t e c t i o n t e c h n i q u e of " n u c l e a r i n d u c t i o n " .
My is a l w a y s n e g a t i v e and h a s i t s m a x i m u m f o r u = uo.
|M J a s a f u n c t i o n of и h a s a b s o r p t i o n s h a p e .
M x is p o s i t i v e f o r u u 0 and z e r o f o r ш = u 0 .
M x a s a f u n c t i o n of и h a s d i s p e r s i o n s h a p e .
With
i i ^ y , maJ
v = M,УI1 " 2
a +b (u-u0)
and
Шп-Ы
u = M^ - c o n s t X 2
a + b (u - wQ )
we can r e p r e s e n t v and u as f u n c t i o n s of и (Fig. 17). If Hj is s m a l l (if

Tj T 2 у H J « 1), we can w r i t e f o r s m a l l R F p o w e r :
T H
- Mv Mo sM i
i T2V"0)2
+
M Т 2 |т1 Н^Цр-и)
l+T2(u-u0)2
M 1-Т^(ц-Шп)2
M* = o
l+Tz2(u-u0)2
194 KASTLER
FIG.18. Rotating magnetic moment in the two frames.
T h e s e e x p r e s s i o n s do not depend on Tj . At r e s o n a n c e M z = M 0 and

M y , „jax = M 0 T 2 | ? | Hj. T h e width at half m a x i m u m of M y is
ш-ш 0 = ± 1 / T 2 o r бы = 2 / T 2 and Sv=6u/2тг = 1/тгТ 2 .
F o r high R F p o w e r , M z max at r e s o n a n c e is r e d u c e d to
M„
M.z, шах = о о
i+^T^H*
where
l + T ^ H *
is the already mentioned "saturation f a c t o r " .

T h e m a x i m u m v a l u e of the a b s o r p t i o n c u r v e b e c o m e s
M„ = МрТаЫн,
"у, max I о о
1
1 + T j Tg 7 H 2
and i t s h a l f - w i d t h is given by
\2 J T2 T2 1
w h e r e (<5ш)2 is a l i n e a r f u n c t i o n of Hj. T h i s e f f e c t is c a l l e d "power

b r o a d e n i n g " . T h e n e g a t i v e s i g n of My s i g n i f i e s t h a t d u r i n g the L a r m o r
p r e c e s s i o n in the x y - p l a n e in t h e l a b o r a t o r y f r a m e , My h a s a phase retardation
of 7t/2 with r e s p e c t to the r o t a t i n g f i e l d Hj, while M x is the rotating com-
ponent of M t in p h a s e with H j if и ш 0 . T h e r o t a t i n g m a g n e t i c m o m e n t is M t = (M x and r e t a r d s with

r e s p e c t to H j by an angle cp given by
My
tan < f o r ш < u,
'0
Mv Т2Ц-и>)
See a l s o F i g . 18. We note that f o r u > u 0 the sign of M x is n e g a t i v e . The

r o t a t i n g field H j e x e r t s on the r o t a t i n g m o m e n t M t a t o r q u e
Г = M, X H ; = |M y | Hj
T h i s t o r q u e is e x e r t e d by the R F field on the s a m p l e c o n t a i n i n g the s p i n s and

can b e m e a s u r e d . The work done by H j on M t is Г m u l t i p l i e d by the angle of
r o t a t i o n , which, p e r unit t i m e , is u . The p o w e r t r a n s m i t t e d f r o m the R F
c i r c u i t to the s u b s t a n c e is
W = Ги = |М I и H j
ц т Ы Hi
W = M, 2
° l + T ^ - u ^ + T ^ H ?
It is m a x i m u m f o r u= u 0 . At t h e " a b s o r p t i o n p e a k " we define:
Wmax = M„0 ц т 2 |т| H!

l+T.T.y2^
T h e s a t u r a t i o n f a c t o r now c o m e s in and, f o r high R F power, W m a x t e n d s to

the a s y m p t o t i c v a l u e
w . м о ц о _ Mp Hp . XQHQ
vv
as » m rp
H T j ^
196 KASTLER
<
и
Q
Z
s:
о
<
>
<
о
67 68 69 70 71
MAGNETIC FIELD IN GAUSS
FIG.20. Resonance curves as obtained by Brossel.
i n d e p e n d e n t of the R F a m p l i t u d e . In t h i s l i m i t i n g c a s e the e n e r g y t r a n s f e r r e d
to the s u b s t a n c e in t i m e Т г is equal to t w i c e the m a g n e t i c e n e r g y s t o r e d in
t h e s u b s t a n c e in t h e c o n s t a n t f i e l d H n
6. RESULTS
Among the t h o u s a n d s of r e s u l t s obtained in r a d i o - f r e q u e n c y s p e c t r o s c o p y ,

we s e l e c t a few t y p i c a l o n e s : .
(a) Study of p u r e Z e e m a n i n t e r v a l s
P u r e e l e c t r o n i c p a r a m a g n e t i s m c o r r e s p o n d s to J f = 0 , I = 0. In a field H 0 ,
a J - l e v e l is split into 2 J + 1 e q u i d i s t a n t m j - s t a t e s (Fig. 19):
E = m H
I igjMB o
IAEA - S M R - 1 2 / 9 197
where
-9П -1
jUg = 0.9274096 X 10 erg • G
±65
The s e l e c t i o n r u l e Д т = ± 1 g i v e s only one r e s o n a n c e f r e q u e n c y c o r r e s p o n d i n g
to Д Е =u 0 fr = у H 0 h = g j P B H 0 . One m e a s u r e s the r a t i o w 0 /H 0 = 7 = gj juB/ii and
d e d u c e s 7, gj and jUj = 7JÏ1. E x a m p l e : the f r e e e l e c t r o n with J = s = The
r e s o n a n c e o c c u r s b e t w e e n the + 1 / 2 and - 1 / 2 s t a t e s .
Q u a n t u m e l e c t r o d y n a m i c s p r e d i c t e d f o r the e l e c t r o n spin a m a g n e t i c
m o m e n t ц 5 ф ц в . ß s = j u B ( l + f ) , w h e r e Ç should be of o r d e r 10" 3 . M e a s u r e -
m e n t s m a d e by K u s c h and F o l e y on bound e l e c t r o n s in a t o m s c o n f i r m e d t h i s
p r e d i c t i o n . M a g n e t i c r e s o n a n c e s on f r e e e l e c t r o n s w e r e obtained by D e h m e l t
u s i n g an o p t i c a l d e t e c t i o n m e t h o d . He c o n f i r m e d the v a l u e of | obtained by
K u s c h . A n o n - R F e x p e r i m e n t d e s i g n e d by C r a n e and r e a l i z e d by h i m and his
collaborators yielded
? = 1.159622 X 10" 3
±27
in good a g r e e m e n t with t h e o r e t i c a l p r e d i c t i o n s :
1 cv су2 15
i T-— + 0.3285 -Я-+ 0.13 -TT + • • • = 1.1596 „
2 -и ti2 7г 39
d e p e n d i n g on the v a l u e adopted f o r the f i n e - s t r u c t u r e c o n s t a n t a . F o r the

e l e c t r o n , ( g - 2 ) / 2 = f . T h i s is c a l l e d the (g-2) a n o m a l y .
In the c a t e g o r y of p u r e e l e c t r o n i c r e s o n a n c e s we c a n r a n g e B r o s s e l ' s
e x p e r i m e n t on E P R of the e x c i t e d s t a t e 6 3 P 1 of the even i s o t o p e s of m e r c u r y .
F o r t h i s s t a t e , J = l , he found g = 1.48 ^ 3 / 2 .
T h e r e s o n a n c e c u r v e s obtained by B r o s s e l a r e shown in F i g . 20.
P u r e n u c l e a r p a r a m a g n e t i s m . If the e l e c t r o n c o n f i g u r a t i o n h a s J = 0, it
is d i a m a g n e t i c : /Uj = 0. If t h e r e i s a n u c l e a r m o m e n t I =/= 0, we o b s e r v e , in a
field HQ, e q u i d i s t a n t n u c l e a r Z e e m a n l e v e l s m : . We c a n u s e f o r the r e s o n a n c e
interval the f o r m u l a
Д Е = u)0fi = H0 = g t pg H 0 = g l V N H 0
where
m MH
rr^- aand
nd в! = Si
Si gT —
m0
w h e r e /uN is t h e n u c l e a r m a g n e t o n . T h e n u c l e a r m o m e n t i s given by
Mi = g r i M B = g ; i ^ N
In g e n e r a l , t h e t a b l e s give (/Lij/pN) = g j l a s the n u c l e a r m o m e n t , in u n i t s of

the nuclear magneton:
juN = 5.050951 X 10" 2 4 e r g - G " 1

±50
198 KASTLER
5.585 MHz
3300 3350 3Í00 3450 3500

И (gaussl
(С)
eu
o<= r „DÔO 1
I
с
] ji*?o4ol
0
FREQL ENCY ,
6.96 MHz
1
i f f
Iii
ЭОО°
лТ I 1 E F
1 3
1625 1650 1675
MAGNETIC FIELD IN GAUSS
FIG. 21. NMR curves as obtained by Rabi.

(a) The 7 Li nucleus in LiCl molecules.
(b) The 19F nucleus in NaF molecules.
(c) Protons in the H2 molecule (orthohydrogen 1=1, J = 1 rotational state).
IAEA-SMR-L2/9 199
FREQUENCY (Hz)
FREQUENCY (Hz)
HG. 22. NMR signals of (a) 19s Hg and (b) 20I Hg (after В. Cagnac, Ann. Phys. (Paris) 6 (1961) 467).
200 KASTLER
FIG. 23. NMR Signal of protons in water.
A s i m p l e e x a m p l e is that of the f r e e n e u t r o n , on which a r e s o n a n c e

e x p e r i m e n t a n a l o g o u s to a Rabi e x p e r i m e n t h a s b e e n m a d e by Bloch and
A l v a r e z . T h e y found f o r this 1 = 1 / 2 p a r t i c l e :
= £n.= _ 1.91280
T h e NMR r e s o n a n c e of o t h e r n u c l e i h a s b e e n o b s e r v e d in d i a m a g n e t i c a t o m i c
ground s t a t e s . F i g u r e 21 s h o w s NMR r e s o n a n c e c u r v e s obtained by Rabi.
By the o p t i c a l m e t h o d , Cagnac found f o r the odd m e r c u r y i s o t o p e s
199
Hg and 2 0 1 Hg:
p 1 9 9 = + 0.497865 Mn I199=J
±6
^201 = * 0.55 1 3 44 mn I = |
±9
^ ä i . = - 1.107416 4
P
l99 ±5
F i g u r e 22 s h o w s r e s o n a n c e c u r v e s f o r 1 9 9 Hg and 201 Hg.

C a g n a c a l s o m e a s u r e d f o r both n u c l e i t h e r e l a x a t i o n t i m e s T]^ in p u r e
m e r c u r y v a p o u r in a f u s e d s i l i c a v e s s e l and found
1QQ 201
T - 3 s T^ - 0.05 s at r o o m t e m p e r a t u r e .
The s t r i k i n g d i f f e r e n c e b e t w e e n the two Тг v a l u e s can b e e x p l a i n e d by the

f a c t t h a t f o r 2 0 1 Hg r e l a x a t i o n o c c u r s by an e l e c t r i c q u a d r u p o l e i n t e r a c t i o n ,
which is a b s e n t in the c a s e of 199 Hg.
P a r a m a g n e t i c n u c l e i in d i a m a g n e t i c m o l e c u l e s a r e in g e n e r a l only
l o o s e l y bound to the m o l e c u l e and behave in an e x t e r n a l f i e l d H 0 , in a f i r s t
a p p r o x i m a t i o n , l i k e f r e e n u c l e i whose m a g n e t i c m o m e n t s c a n b e d e t e r m i n e d
by NMR e x p e r i m e n t s . E x a m p l e s : 7 L i in L i C l , o r ^ in KOH, o r p r o t o n s
IAEA - S M R - 1 2 / 9 201
in liquid w a t e r . F o r p r o t o n s in w a t e r or in o r g a n i c m o l e c u l e s t h e l o c a l f i e l d
c r e a t e d by the m o l e c u l a r s u r r o u n d i n g a d d s t o t h e e x t e r n a l f i e l d . A d i a m a g n e t i c
c o r r e c t i o n h a s t o b e a p p l i e d to c a l c u l a t e t h e t r u e p r o t o n m o m e n t .
F i g u r e 23 s h o w s an NMR s i g n a l of p r o t o n s in w a t e r .
Without t h i s c o r r e c t i o n f o r p r o t o n s in w a t e r , one m e a s u r e s
7 ' = 26 751.270 and |eL = ZjL = 4.257597 k H z - G _ 1

H
±80 ° ±13
W i t h the d i a m a g n e t i c c o r r e c t i o n we g e t :
26 751.965 and = 4.257705 k H z - G '

27Г
±80 ±13
This gives
ÍÍL = 1 2.792782
±17
T h e p r o t o n m o m e n t ц р h a s a l s o b e e n c o m p a r e d d i r e c t l y with t h e B o h r m a g -
neton :
^ = 1.52103264 X 10" 3
йв
±50
T h e c a s e of t h e H 2 m o l e c u l e s t u d i e d by the R a b i m e t h o d i s i n t e r e s t i n g .
T h e f i n e s t r u c t u r e of i t s NMR s i g n a l g i v e s i n f o r m a t i o n on t h e m a g n e t i c
i n t e r a c t i o n s in t h e m o l e c u l e . It c o r r e s p o n d s t o the J = 1 r o t a t i o n a l l e v e l of
o r t h o h y d r o g e n (I 1 + I 2 = 1). See F i g . 21c.
P a r a m a g n e t i c i o n s d i l u t e d in a d i a m a g n e t i c s o l v e n t or in d i l u t e d c r y s t a l s
a l s o b e h a v e , in f i r s t a p p r o x i m a t i o n , like f r e e m a g n e t s in t h e e x t e r n a l f i e l d H 0 ,
and t h e i r g - f a c t o r c a n be d e t e r m i n e d . F i g u r e 24 s h o w s a r e s o n a n c e s i g n a l of
Mn + + o b s e r v e d by Z a v o i s k y . He o b t a i n e d g «2. But n o t e t h a t in t h i s c a s e t h e
r e s o n a n c e s i g n a l is l a r g e , the r e l a x a t i o n t i m e T2 being v e r y s m a l l .
(b) T h e f i n e - s t r u c t u r e i n t e r v a l s of t h e n= 2 l e v e l of t h e h y d r o g e n a t o m .
The Lamb shift
T h e l e v e l n = 2 of t h e h y d r o g e n a t o m c o n t a i n s t h r e e f i n e s t r u c t u r e l e v e l s :
2 2 SI/2 ( m e t a s t a b l e ) , 2 2 P ц 2 and 2 2 P 3 / 2 . T h e e n e r g y d i f f e r e n c e b e t w e e n the
two P l e v e l s is o b s e r v e d in t h e f i n e s t r u c t u r e of t h e o p t i c a l H a l i n e . It i s of
t h e o r d e r Д с т ~ 0 . 3 3 c m - 1 ~ 10 GHz. A c c o r d i n g to D i r a c ' s t h e o r y , t h e two
l e v e l s 2 2 S 1 / 2 and 2 2 P 1 / / 2 s h o u l d b e d e g e n e r a t e . T h e y a r e n o t . L a m b and
R e t h e r f o r d (1948) h a v e m e a s u r e d t h e i r d i s t a n c e by s t u d y i n g t h e r e s o n a n c e
b e t w e e n t h e m j s t a t e s of S i / 2 and P i / 2 - ( F i g . 25). T h e s e t r a n s i t i o n s a r e e l e c t r i c
d i p o l e t r a n s i t i o n s . T h e r e s u l t of t h e i r m e a s u r e m e n t i s
2 2 S 1 / 2 - 2 2 P 1 / 2 = 1.059 004 GHz

±10
202 KASTLER
H (Oel
FIG.24. EPR signals obtained by Zavoisky (1945).
(a) EPR signal of M n H ions in S0 4 Mn at 2.75 GHz;
(b) EPR signal of C r + + + ions in CrCl s at 2.19 GHz and
(c) 2.76 GHz.
IAEA - S M R - 1 2 / 9 2 0 3
дм=о
ctě
_
l\
I\
(b) 20 -
дм=1
\
I \
УV
af
I I\
7
1 1 г"
1000 1200 1400 1600
GAUSS
FIG.25. Z e e m a n splitting and resonance signals.

2
(a) Z e e m a n splitting in magnetic field (abscissa, units of 5214 G) of the fine-structure states 2 P3/2.
2 2 S j / 2 and 2 2 Pj д of the hydrogen a t o m ;
(b) resonance signals :
a f 2 tS1/2. m = + 1 / 2 — 2 гР1/г, m = - 1 / 2
et e 2 %/г, m = + 1/2—> 2 г ? 1 / г , m = + 1/2 (after Lamb and Retherford).
It is c a l l e d the " L a m b s h i f t " and h a s b e e n explained by q u a n t u m e l e c t r o -

dynamics.
(c) H y p e r f i n e s t r u c t u r e s in a t o m i c g r o u n d s t a t e s
T h e h y p e r f i n e s t r u c t u r e (HFS) of a t o m i c e n e r g y s t a t e s is a r e s u l t of the
i n t e r a c t i o n b e t w e e n the e l e c t r o n c o n f i g u r a t i o n of the a t o m and the n u c l e a r
m o m e n t s . It o c c u r s if the n u c l e a r spin v a l u e I is d i f f e r e n t f r o m z e r o .
204 KASTLER
z
T A B L E I. H Y P E R F I N E I N T E R V A L S IN GROUND S T A T E S1/2 OF
H Y D R O G E N AND A L K A L I A T O M S
Atom Nuclear spini v t (MHz)
>H 1/2 1420.40 5 a

2
H 1 327.384
6
Li 1 228.22
7
Li 3/2 803.54
22 c
Na 3 1 220.6
23
Na 3/2 1771.75
39K 3/2 461.75
«кс 4 1285.7
41K 3/2 254.02
85
Rb 5/2 3 035.73
<"Rb 3/2 6 834.70

133
Cs 7/2 9192.7b
13
fcs C 7/2 9 724
137 c
Cs 7/2 10 126
a
This is the line of the hydrogen maser. It is also the emission line observed in radio-astronomy,
b This is the line of the caesium atomic clock which defines the time-unit.
c
Radioactive isotopes.
We h a v e s e e n t h a t an a t o m i c e n e r g y s t a t e h a s a c h a r a c t e r i s t i c J - v a l u e ,
t h e a n g u l a r m o m e n t u m of the e l e c t r o n c o n f i g u r a t i o n in t h i s s t a t e i s P = J h
and t h e a s s o c i a t e d m a g n e t i c m o m e n t i s Hj = g JjUb w h e r e ц в i s the B o h r
m a g n e t o n and g t h e L a n d é - f a c t o r of t h e s t a t e . If a n u c l e a r s p i n 1 ^ 0 e x i s t s ,
t h e a n g u l a r m o m e n t u m of the n u c l e u s I h is a l s o a s s o c i a t e d t o a n u c l e a r
m a g n e t i c m o m e n t jU; w h i c h i s v e r y s m a l l and e x p r e s s e d in n u c l e a r m a g n e t o n s
HN a s we h a v e s e e n . T h e i n t e r a c t i o n b e t w e e n t h e t w o m o m e n t s n j and щ
g i v e s r i s e t o a c o u p l i n g e n e r g y which c a n b e e x p r e s s e d b y
A i s c a l l e d the h y p e r f i n e c o u p l i n g c o n s t a n t . T h e r e s u l t i s t h a t e a c h e n e r g y
l e v e l J i s s p l i t i n t o 21 + 1 " h y p e r f i n e s u b l e v e l s " w h i c h a r e d e s i g n e d by a
h y p e r f i n e q u a n t u m n u m b e r F w h i c h c a n t a k e 21 + 1 d i f f e r e n t v a l u e s — d i f f e r i n g
b y u n i t y — b e t w e e n J - l a n d J + l . (In t h e c a s e w h e r e J < I , t h e two n u m b e r s
J and I h a v e t o be i n t e r c h a n g e d . ) F o r e x a m p l e , in t h e c a s e of the h y d r o g e n
a t o m and of t h e a l k a l i a t o m s , t h e g r o u n d s t a t e 2S^ h a s J = f and t h e t w o F - v a l u e s
a r e F - p I + i and F 2 = I - i . T h e e n e r g y d i f f e r e n c e b e t w e e n t h e s e t w o s t a t e s
Ep - Ep i s c a l l e d the " h y p e r f i n e i n t e r v a l " , and i t s r e s o n a n c e f r e q u e n c y
v0 - (Ep - Ep ) / h i s a c h a r a c t e r i s t i c f r e q u e n c y of e a c h a t o m i c s p e c i e s . S o m e
of t h e s e f r e q u e n c i e s a r e g i v e n in T a b l e I.
T r a n s i t i o n s b e t w e e n t h e s e F - l e v e l s a r e o b s e r v e d in r a d i o - f r e q u e n c y
spectroscopy.
IAEA - S M R - 1 2 / 9 205
H y p e r f i n e s t r u c t u r e s have b e e n s t u d i e d , e s p e c i a l l y by the Rabi m e t h o d ,

in the ^ j / g ground s t a t e s of a l l a l k a l i and f o r t h e d i f f e r e n t i s o t o p e s of
h y d r o g e n . T h e evolution of the m F s t a t e s of t h e s e J = 1 / 2 l e v e l s in an e x t e r n a l
f i e l d H0 is given by the B r e i t - R a b i f o r m u l a .
F o r e x a m p l e f o r 1 3 3 C s , 1 = 7 / 2 and t h e two F - l e v e l s a r e F j = 1+ 1/2 = 4
and F 2 = I - 1 / 2 = 3. T h e i r gF f a c t o r s in s m a l l f i e l d s a r e
gj 2 _ 1_
G
FJ " " G
F 2 " 21 + 1 " 8 " 4
T h e f r e q u e n c y i n t e r v a l b e t w e e n the two F - s t a t e s c o r r e s p o n d i n g to ДЕ 0 = hv 0
in a z e r o m a g n e t i c field h a s b e e n a c c u r a t e l y m e a s u r e d and can be d e t e r m i n e d
in the a t o m i c clock u s i n g c a e s i u m a t o m s to d e f i n e the t i m e unit.
T h e p r e s e n t unit of t i m e , one s e c o n d , is b a s e d on the convention
v. ( 1 3 3 Cs ) = 9 192 631 770.00 Hz
T h i s is the f r e q u e n c y m e a s u r e d b e t w e e n the two Z e e m a n s u b l e v e l s ( F , m p ) :

(4, 0) 2 (3, 0). T h i s f r e q u e n c y s h o w s a q u a d r a t i c d e p e n d e n c e on the f i e l d
Ho ' v o,o ' vo +427 H 2 • (Hz- G~2), while t h e o t h e r h y p e r f i n e t r a n s i t i o n s depend
l i n e a r l y on t h e f i e l d v a l u e .
C o n s t r u c t i n g a h y d r o g e n m a s e r , R a m s e y and c o - w o r k e r s have
m e a s u r e d , in this unit, t h e HFS i n t e r v a l s of h y d r o g e n and of t r i t i u m :
7H = 1 4 2 0 4 0 5 751.864
±1
7 = 1 516 701 470.808

T
±7
^ L = 1.067 794 514 973

7
H ±5 (10" 12 )
T h i s is p r o b a b l y the h i g h e s t p r e c i s i o n e v e r obtained in any p h y s i c a l m e a s u r e m e n t .

We m a y c o m e b a c k to Mn ++ ions at high dilution w h e r e a h y p e r f i n e s t r u c -
t u r e a p p e a r s with s i x p e a k s : 21 + 1 = 6, i n d i c a t i n g that 1 = 5 / 2 f o r t h e M n n u c l e u s
(Fig. 26).
(d) T h e m u o n i u m e /u+
M u o n i u m was d i s c o v e r e d by V e r n o n Hughes in 1957 and is an a t o m i c

s y s t e m f o r m e d by a p o s i t i v e j u - m e s o n which h a s c a p t u r e d an e l e c t r o n . It can
b e c o n s i d e r e d as a light i s o t o p e of h y d r o g e n and h a s in i t s ground s t a t e , like
h y d r o g e n , two h y p e r f i n e l e v e l s , F = 1 and F = 0. In a f i e l d H 0 the Z e e m a n
s p l i t t i n g s a r e given by a B r e i t - R a b i f o r m u l a ( F i g . 27). T h e muon m a s s
c o m p a r e d with that of the e l e c t r o n is т д / т е = 206.761 ± 0.005, the r e d u c e d
m a s s is l / й = 1/m^ + l / m e , and the R y d b e r g c o n s t a n t is RM = 109 209.12 cm" 1 ,
206 KASTLER
Л i, N
л 2 N
л
FIG.26. Paramagnetic resonance signals of Mn + + ions in aqueous solutions of S0 4 Mn. From top to bottom
concentration is reduced (N = normal solution) and ahyperfine structure with six peaks appears. 21 + 1 = 6,
nuclear spin of 55Mn : 1 = 5/2 (after Schneider and England).
c o m p a r e d with R H = 109 677.58 c m - 1 . The two h y p e r f i n e l e v e l s a r e s e p a r a t e d

by an i n t e r v a l p r e d i c t e d by c a l c u l a t i o n :
„ = I i ö 2 c ^ R » 4.524 GHz
0 h 3 'ue "
C o r r e c t i o n s of q u a n t u m e l e c t r o d y n a m i c s give vQ =4.46316 GHz. The B r e i t -
Rabi f o r m u l a c a n be w r i t t e n
ДЕ, AE„
E.F, mE
1 + 2 т р х + х"
with
(g - g )ц H
and x =
ДЕ,'о
T h e d e t e c t i o n of R F r e s o n a n c e s of m u o n i u m i s b a s e d on the following
f a c t s : T h e m u o n is p r o d u c e d by stopping pions c o m i n g f r o m a s y n c h r o -
c y c l o t r o n in a r g o n gas:
7г+ -*• + neutrino
The h a s i t s spin v e c t o r a n t i p a r a l l e l to the v e l o c i t y v e c t o r of t h e ir*, and

the f i e l d H 0 i s applied p a r a l l e l t o this s p i n v e c t o r , s o т д = + 1 / 2 . A f t e r a
m e a n life of 2.2 X 10" 6 s , the d e c a y s to
-* e + + n e u t r i n o s
T h e r e is an a s y m m e t r y of p o s i t r o n e m i s s i o n , the e m i s s i o n b e i n g f a v o u r e d
in the d i r e c t i o n of the /u+ spin (positive d i r e c t i o n of H 0 ). This is equivalent
to n u c l e a r o r i e n t a t i o n of the m u o n i u m p r o d u c e d . D i f f e r e n t c o u n t e r s m e a s u r e
IAEA - S M R - 1 2 / 9 207
m 3 = *'/2- m u =*V2
m, = • V2. nv-1/!
• mj e - ' / î . = - y2
FIG.27. Zeeman splitting in field H, as given by Breit-Rabi formula.
t h e n u m b e r of p o s i t r o n s e m i t t e d in the + H 0 and - H 0 d i r e c t i o n s . If by a
m a g n e t i c r e s o n a n c e the ц* spin is r e v e r s e d , the counting r a t e i s changed.
T h i s e f f e c t is u s e d to m o n i t o r t h e r e s o n a n c e and to d e t e r m i n e i t s f r e q u e n c y in
a f i e l d HQ. R F r e s o n a n c e s in h i g h - f i e l d (rrij,m^) and in l o w - f i e l d conditions
( F , m p ) h a v e b e e n o b s e r v e d by Hughes and h i s c o - w o r k e r s . T h e y give the
experimental values
i/Q = 4463.15 ± 0.06 MHz f r o m h i g h - f i e l d m e a s u r e m e n t s ,
and
v'o = 4463.18 ± 0.12 MHz f r o m l o w - f i e l d m e a s u r e m e n t s ,
which a r e in e x c e l l e n t a g r e e m e n t with quantum e l e c t r o d y n a m i c s .

The e x p e r i m e n t a l c o n d i t i o n s a r e the following:
(a) H i g h - f i e l d r e s o n a n c e : HQ= 5 400 g a u s s x=3.4, resonance frequency

l o c a t e d b e t w e e n 1.83 and 1.84 GHz
(b) Low-field resonance: H0=2.7 gauss
One o b s e r v e s in t h i s c a s e the t r a n s i t i o n s 1,1 ->0,0 and 1 , - 1 -» 0,0. T h e

r e s o n a n c e s a r e o b s e r v e d at d i f f e r e n t a r g o n p r e s s u r e s and one h a s to e x t r a -
p o l a t e to t h e z e r o - p r e s s u r e v a l u e .
(e) Positronium
T h i s is a s y s t e m f o r m e d by a p o s i t i v e e l e c t r o n e + and a n e g a t i v e
e l e c t r o n e". Its e x i s t e n c e w a s s u g g e s t e d by M o h o r o v i c i č in 1934. It w a s
d i s c o v e r e d by M a r t i n D e u t s c h (1951) in the annihilation p r o c e s s of p o s i t r o n s
in g a s e s , w h e r e a p r e s s u r e - i n d e p e n d e n t h a l f - l i f e of the o r d e r of 10" 7 s w a s
found. I t s B o h r l e v e l s a r e given by E n = (Rhc/n 2 ) and i t s B o h r r a d i u s i s
t w i c e that of h y d r o g e n . In i t s g r o u n d level n = 1 it e x i s t s in two d i f f e r e n t
s t a t e s , both with L = 0 (S s t a t e s ) . T h e notation u s e d f o r t h e m is 3 S j and 1 S Q .
F o r t h e o r d i n a r y , n e g a t i v e e l e c t r o n , the a n g u l a r m o m e n t u m p and the
m a g n e t i c m o m e n t ц a r e o p p o s i t e , f o r the p o s i t i v e e l e c t r o n o r p o s i t r o n , t h e
two v e c t o r s have the s a m e d i r e c t i o n .
208 KASTLER
NEGATIVE ELECTRON POSITIVE ELECTRON
P>
111
- * HI-
J
STATE S, STATE S0
OF POSITRONIUM OF POSITRONIUM
1-Й
I—
P, P2=0
Pi * P2 = 1
Ï , • M-2 = 0 Ï , + il2= 1
ORTHO- POSITRONIUM PARA-POSITRONIUM
FIG-28. Formation of ortho- and parapositronium.
If the two p a r t i c l e s c o m b i n e to f o r m p o s i t r o n i u m , they can do it in two

d i f f e r e n t m a n n e r s (Fig. 28):
(a) T h e two a n g u l a r m o m e n t a a r e p a r a l l e l , and in this c a s e the two m a g n e t i c
m o m e n t s a r e a n t i p a r a l l e l . The r e s u l t a n t a n g u l a r m o m e n t u m is
!*+!*=ft
which c o r r e s p o n d s to a s t a t e J = 1 o r a 3 S 1 s t a t e . The r e s u l t a n t m a g n e t i c
m o m e n t is z e r o . T h i s s t a t e is c a l l e d t h e " o r t h o - p o s i t r o n i u m " s t a t e .
(b) T h e two a n g u l a r m o m e n t a a r e o p p o s i t e in d i r e c t i o n and t h e two m a g n e t i c
m o m e n t s have the s a m e d i r e c t i o n :
which c o r r e s p o n d s to a s t a t e J = 0 o r a 1 S 0 s t a t e . Its r e s u l t a n t m a g n e t i c
m o m e n t i s e q u a l to two B o h r m a g n e t o n s . T h i s s t a t e is c a l l e d the
"para-positronium" state.
F i g u r e 29 shows the d i f f e r e n c e of e n e r g y of t h e s e two s t a t e s and t h e i r

b e h a v i o u r in a m a g n e t i c field HQ.
In i t s s i n g l e t s t a t e with opposite s p i n s , p o s i t r o n i u m c a n d e c a y by a
t w o - p h o t o n p r o c e s s , both photons having the e n e r g y E = hv = 0.5 MeV. To
t h i s d e c a y c o r r e s p o n d s a l i f e t i m e of L25 X 1 0 " 1 0 s . In i t s t r i p l e t s t a t e ,
p o s i t r o n i u m can d e c a y only by a t h r e e - p h o t o n p r o c e s s w h o s e p r o b a b i l i t y is
m u c h s m a l l e r and c o r r e s p o n d s to a l i f e t i m e of 1.4 X 10" 7 s .
IAEA - S M R - 1 2 / 9 209
FIG.29. Energy difference of ortho- and parapositronium, behaviour in a magnetic field.
P h o t o n s of e n e r g y s m a l l e r than 0.5 MeV, e s p e c i a l l y in t h e r a n g e

0.38 MeV, c a n o r i g i n a t e only in t h e t h r e e - p h o t o n p r o c e s s . The e n e r g y
i n t e r v a l ДЕ0 b e t w e e n the two s t a t e s is of the o r d e r of
г л 2 у ц2
AE =—TT/Ligl^ (0) = - í - j = 204.4 GHz
a
o
T a k i n g into a c c o u n t t h e q u a n t u m e l e c t r o d y n a m i c a l c o r r e c t i o n s , this v a l u e i s
changed to
A E 0 / h = 203.37 GHz (A = 1.5 m m )
G e n e r a t o r s of t h i s high f r e q u e n c y a r e not a v a i l a b l e . By applying a f i e l d H 0 ,

the two s t a t e s (1,0) and (0,0) a r e m i x e d . T h e a d m i x t u r e of the s i n g l e t s t a t e
to (1,0) s h o r t e n s t h e l i f e t i m e of the l a t t e r .
An R F r e s o n a n c e at 3 GHz in a field n e a r 9000 g a u s s p r o d u c e s the
transitions
(1, ± 1 ) - (1, 0)
and f a v o u r s the t w o - p h o t o n d e c a y p r o c e s s . T h e r e s o n a n c e c a n be m o n i t o r e d
by c o u n t e r s . T h i s R F e x p e r i m e n t m a d e in 1952 by D e u t s c h and Brown g i v e s
the r e s u l t :
v0 = ДЕд/h = 203.2 ± 0.3 GHz,
in good a g r e e m e n t with q u a n t u m e l e c t r o d y n a m i c s .
210 KASTLER
7. CONCLUSION
A s e r i e s of f e a t u r e s of R F S w e r e not m e n t i o n e d , f o r e x a m p l e the
i m p o r t a n c e of h i g h - r e s o l u t i o n NMR f o r p r o b l e m s of c h e m i c a l s t r u c t u r e , o r
t h e m e t h o d s of d y n a m i c o r i e n t a t i o n of n u c l e i , y i e l d i n g p o l a r i z e d b e a m s and
polarized targets for nuclear-physics experiments.
T h e e n o r m o u s a m o u n t of work done on E P R and NMR in liquids and s o l i d s
h a s t h r o w n light on s o l i d - s t a t e s t r u c t u r e s and on the b e h a v i o u r of p a r a -
m a g n e t i c ions and n u c l e i in condensed m a t e r i a l . R F S h a s found i t s
a p p l i c a t i o n s a l s o in r a d i o a s t r o n o m y . T h e line of a t o m i c h y d r o g e n at
1420 MHz (X = 21 c m ) i s o b s e r v e d as e m i s s i o n , line f r o m t h e h y d r o g e n c l o u d s
in the g a l a x y . I t s s y s t e m a t i c study h a s given i n f o r m a t i o n on the s p i r a l
s t r u c t u r e of our galaxy. O t h e r l i n e s , of the r a d i c a l OH and the w a t e r
m o l e c u l e , a r e o b s e r v e d in e m i s s i o n . L i n e s of m a n y r a d i c a l s and m o l e c u l e s
a r e o b s e r v e d in a b s o r p t i o n and show that t h e s e m o l e c u l e s a r e p r e s e n t in
i n t e r s t e l l a r s p a c e w h e r e they a r e p r o b a b l y s y n t h e s i z e d by p h o t o c h e m i c a l
reactions.
Let u s f i n a l l y m e n t i o n s o m e s p e c i a l l i t e r a t u r e that m a y be of i n t e r e s t
f o r the r e a d e r . In the f i e l d of m o l e c u l a r b e a m s we r e f e r to the a r t i c l e by
J . B. K e l l o g and S. M i l l m a n , " T h e m o l e c u l a r b e a m m a g n e t i c r e s o n a n c e
m e t h o d " , (Rev. Mod. P h y s . 1_8 (1946) 323) o r the book by N. F . R a m s e y ,
M o l e c u l a r B e a m s , C l a r e n d o n P r e s s (1956).
As r e g a r d s n e u t r o n NMR let us m e n t i o n F . Bloch, P h y s . Rev. 74^ (1948)
1025; s e e a l s o N. F . R a m s e y , P h y s . Rev. 179 (1969) 1285. F o r E P R we
r e c o m m e n d the book by A. A b r a g a m and B. B l e a n e y , E l e c t r o n P a r a m a g n e t i c
R e s o n a n c e of T r a n s i t i o n I o n s , C l a r e n d o n P r e s s (1970). D e t a i l s on the
L a m b s h i f t m a y b e found in W. L a m b , Rep. P r o g . P h y s . _14 (1951) 19, and on
the (g-2) a n o m a l y of t h e e l e c t r o n in H. R. C r a n e and D. T. W i l k i n s o n , P h y s .
R e v . 130 (1963) 852. As to optical m e t h o d s s e e R. B e r n h e i m , O p t i c a l
P u m p i n g , B e n j a m i n (1965); C. C o h e n - T a n n o u d j i and A. K a s t l e r , O p t i c a l
p u m p i n g " , in P r o g r e s s in O p t i c s , N o r t h Holland (1966) o r A . K a s t l e r , " O p t i c a l
m e t h o d s f o r the study of r a d i o f r e q u e n c y r e s o n a n c e s " , P h y s . Today 20^
(1967) 34. As r e g a r d s m u o n i u m and p o s i t r o n i u m we r e f e r to V . W . H u g h e s ,
" M u o n i u m " , Annu. Rev. Nucl. Sei. (1966) 445; F . J . M. F a r l e y , " E l e c t r o -
m a g n e t i c p r o p e r t i e s of the m u o n " , P r o g . Nucl. P h y s . 9^ (1964) 257 (see
pp. 263 and 281); M. D e u t s c h , "Annihilation of p o s i t r o n s " , P r o g . Nucl.
P h y s . 3^ (1956) 131.
In t h e f i e l d of r a d i o a s t r o n o m y we have to m e n t i o n M. Ryle, " R a d i o
a s t r o n o m y " , Rep. P r o g . P h y s . j_3 (1950) 184 and B. L o v e l l and J . A. Cleog,
Radio A s t r o n o m y , C h a p m a n and Hall (1952).
BIBLIOGRAPHY
GORTER, C . J . , Paramagnetic Relaxation, Elsevier (1947).
ABRAGAM, A . , The Principles of Nuclear Magnetism, Clarendon Press (1961).
TOWNES, C . H . , SCHAWLOW, A . L . , Microwave Spectroscopy, McGraw-Hill (1955),
GORDY, W., COOK, R.L., Microwave Molecular Spectra, J. Wiley (1970).
STRANDBERG, M.W. P., Microwave Spectroscopy McGraw-Hill (1955).

IAEA - S M R - 1 2 / 9 211
BLEANEY, В., The radiofrequency spectroscopy of gases. Rep.Prog.Phys. 20 (1948) 668.
INGRAM, D . J . E . , Spectroscopy at Radio and Microwave Frequencies, Butterworths (1955).
ANDREW, E.R., Nuclear Magnetic Resonance, Cambridge University Press (1955).
PAKE, G . E . , Paramagnetic Resonance, Benjamin (1962).
STEPIN, L . D . , Quantum Radio Frequency Physics, transi, from Russian, MIT Press (1963-65).
ALTSCHULER, S . A . , KOZYREV, B.M., Electron Paramagnetic Resonance, transi.from Russian, Academic

Press (1964).
BLOEMBERGEN, N . . Nuclear Magnetic Relaxation. Benjamin (1961).
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RAMSEY, N . F . , "Nuclear moments", in Experimental Nuclear Physics, Ed. SEGRE, E., J. Wiley (1960) 358.
JEFFRIES, C . D . , Dynamic Nuclear Orientation, J. Wiley (1963).
BENEDEK, G.B., Magnetic Resonance at High Pressures, J. Wiley (1963).
DAS, T . P . , HAHN, E.L., Nuclear Quadrupole Resonance Spectroscopy, Academic Press (1958).
Proceedings of the International Conference on Paramagnetic Resonance, Ed. LOW, W., Jerusalem,
July 1962, Academic Press (1963).
Advances in Magnetic Resonance, 5 volumes, Ed. WAUGH, J . S . , Academic Press (1965-71).
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Masson, Paris (1965, 1969).
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LOESCHE, A . , Kerninduktion (Deutsch. Verlag der Wiss., Berlin, DDR (1957))•
BRAUNBEK, W., Hochfrequenzspektroskopie, Naturwissenschaften 36 (1949) 98, 338.

IAEA - S M R - 1 2 / 7
NUCLEAR E F F E C T S IN ATOMIC SPECTRA

J. BAUCHE
Laboratoire Aimé Cotton,
Orsay, France
Abstract
NUCLEAR EFFECTS IN ATOMIC SPECTRA.

Hyperfine structure ; line structure interpretation; electromagnetic properties of the nucleus; theory of
magnetic-dipole hyperfine structure (sublevels, transitions); electric-quadrupole hyperfine structure; hyperfine-
structure constants; configuration interaction; hyperfine-structure anomaly.
Isotope shift theory; co-existence of mass and field isotope shift; order-of-magnitude estimates;
King graphs; theoretical approaches.
P A R T I: HYPERFINE STRUCTURE
1. INTRODUCTION
T h i s p a p e r a i m s at d e s c r i b i n g two a t o m i c p h e n o m e n a , h y p e r -
f i n e s t r u c t u r e and i s o t o p e s h i f t , w h o s e s t u d y h a s b e e n f o r m a n y y e a r s
e x t r e m e l y u s e f u l f o r the k n o w l e d g e of n u c l e i and a t o m i c s t r u c t u r e .
T h e g r o s s p h e n o m e n o n we a r e i n t e r e s t e d in i s t h e f o l l o w i n g . W h e n
o b s e r v e d with a h i g h - r e s o l u t i o n s p e c t r o m e t e r (see p a p e r by P . Jacquinot),
e a c h a t o m i c s p e c t r a l l i n e of a g i v e n e l e m e n t r e v e a l s a " h y p e r f i n e " s t r u c t u r e ,
i. e. it a p p e a r s t h a t it i s in f a c t a g r o u p of s e v e r a l c o m p o n e n t s v e r y c l o s e •
to one a n o t h e r : F o r m o s t l i n e s t h e t o t a l w i d t h of t h e s t r u c t u r e i s of the o r d e r
of 10 m i l l i k a y s e r s (10 m K ; 1 m K = 1 0 " 3 K > l O ^ c m " 1 ) , t o a f a c t o r of 100 in
both directions.
It is w e l l known t h a t e a c h n a t u r a l c h e m i c a l e l e m e n t i s g e n e r a l l y a b l e n d
of s e v e r a l s t a b l e i s o t o p e s . One r e a s o n f o r the s t r u c t u r e o b s e r v e d i s t h a t the
l i n e d u e t o the t r a n s i t i o n b e t w e e n a g i v e n p a i r of e l e c t r o n i c l e v e l s h a s not
exactly the s a m e wave n u m b e r f o r all isotopes, as m a y be expected a p r i o r i .
This phenomenon is called "isotope shift".
By m e a n s of m a s s s p e c t r o g r a p h s , n u c l e a r p h y s i c i s t s c a n s e p a r a t e i n t o
p u r e i s o t o p e s a p p r e c i a b l e a m o u n t s of e v e r y e l e m e n t . In t h e a t o m i c l i n e s of
s u c h a n i s o t o p e , t h e r e m a y s t i l l a p p e a r s t r u c t u r e s , e s s e n t i a l l y in a l l c a s e s
of i s o t o p e s w i t h a n odd m a s s n u m b e r A. T h i s p h e n o m e n o n is p r o p e r l y c a l l e d
"hyperfine structure".
2. HYPERFINE STRUCTURE
2.1. I n t e r p r e t a t i o n of l i n e s t r u c t u r e s
T h e i n t e r p r e t a t i o n of t h e h y p e r f i n e s t r u c t u r e (hfs) p h e n o m e n o n a s a r i s i n g
f r o m t h e e x i s t e n c e of t h e n u c l e a r s p i n a n g u l a r m o m e n t u m w a s s u g g e s t e d by
P a u l i in 1924. In w h i c h way d o e s t h i s s p i n a f f e c t a t o m i c l i n e s ?
213
214 BAUCHE
Nowadays we know that a n u c l e u s is not an e l e m e n t a r y p a r t i c l e (except

the p r o t o n , t h e H 1 n u c l e u s ) but an n - p a r t i c l e s y s t e m , whose s t r u c t u r e h a s
b e e n s t u d i e d e x t e n s i v e l y f o r m a n y y e a r s . In p r i n c i p l e , we should c o n s i d e r
f o r t h e a t o m , i n s t e a d of the c l a s s i c a l p r o b l e m of one n u c l e u s and Z e l e c t r o n s ,
that of Z p r o t o n s , A - Z n e u t r o n s and Z e l e c t r o n s .
But t h i s i n c r e a s e in c o m p l e x i t y c a n b e avoided with t h e help of the B o r n -
O p p e n h e i m e r t h e o r e m . T h i s quantum t h e o r e m , which is of f u n d a m e n t a l
i m p o r t a n c e in m o l e c u l a r s p e c t r o s c o p y , a g r e e s in p a r t i c u l a r with the following
c l a s s i c a l i d e a s . C o n s i d e r two s y s t e m s of p a r t i c l e s , with i n t e r a c t i o n s b e t w e e n
p a r t i c l e s i n s i d e s y s t e m 1, i n s i d e s y s t e m 2 and b e t w e e n both s y s t e m s . If t h e
i n t e r a c t i o n s i n s i d e , s a y , s y s t e m 1 a r e s t r o n g enough f o r the r e v o l u t i o n
p e r i o d s of its p a r t i c l e s to be m u c h s h o r t e r than t h o s e in s y s t e m 2, a t i m e -
a v e r a g e d d e s c r i p t i o n of s y s t e m 1 is s u f f i c i e n t f o r studying t h e m o t i o n s of the
p a r t i c l e s of s y s t e m 2. In quantum l a n g u a g e , t h e r e v o l u t i o n t i m e is p r o p o r -
t i o n a l to the i n v e r s e of the e n e r g y . As we know t h a t t h e e n e r g i e s in n u c l e a r
p r o b l e m s a r e m e a s u r e d in MeV ( 10 6 eV), in c o n t r a s t with t h o s e in a t o m i c
s p e c t r o s c o p y (1 eV c o r r e s p o n d s to 8066 cm" 1 ), we conclude that a t i m e -
a v e r a g e d d e s c r i p t i o n of the n u c l e u s is a l l we n e e d , in a f i r s t and e x c e l l e n t
approximation.
2.1.1. E l e c t r o m a g n e t i c e x t e r n a l p r o p e r t i e s of the n u c l e u s
A n u c l e u s is b u i l t up of n u c l é o n s ( p r o t o n s and n e u t r o n s ) . E l e c t r o n s
i n t e r a c t with t h e n u c l e u s a l m o s t only t h r o u g h t h e C o u l o m b f u n d a m e n t a l f o r c e
(no n u c l e a r s t r o n g i n t e r a c t i o n b e t w e e n e l e c t r o n s and n u c l é o n s ; g r a v i t a t i o n a l
f o r c e c o m p l e t e l y n e g l i g i b l e ; n u c l e a r weak i n t e r a c t i o n n e g l i g i b l e ) . T h i s f o r c e
l e a d s to e l e c t r o s t a t i c and m a g n e t i c e f f e c t s . As the s p a t i a l e x t e n s i o n of the
n u c l e u s i s m u c h s m a l l e r than the a t o m i c d i m e n s i o n s , we can w r i t e the n u c l e a r
e l e c t r o s t a t i c and m a g n e t i c p o t e n t i a l s a s e x p a n s i o n s in t e r m s of r , t h e d i s t a n c e
to the c e n t r e of the n u c l e u s .
A s i m p l i f y i n g p r o p e r t y is t h e following. It is. known [1] that
p a r i t y is a good quantum n u m b e r f o r a t o m i c ( e l e c t r o n i c ) s t a t e s . If we n e g l e c t
the i n f l u e n c e of the s m a l l — but famous'. — weak n u c l e a r f o r c e s , which
v i o l a t e p a r i t y c o n s e r v a t i o n , p a r i t y is a l s o a good quantum n u m b e r f o r n u c l e a r
s t a t e s . It can be e a s i l y d e d u c e d that m u l t i p o l e s of odd (even) r a n k do not
o c c u r in t h e e l e c t r o s t a t i c (magnetic) e x p a n s i o n .
(a) E l e c t r o s t a t i c expansion
T h e l e a d i n g t e r m in the e x p a n s i o n of the e l e c t r o s t a t i c p o t e n t i a l in M, due

to the p r o t o n s only, is (1/47re 0 )(Ze/r)(e = 1.6 X 10" 1 9 Coulomb): the e l e c t r o -
s t a t i c m u l t i p o l e of r a n k 0 is the c h a r g e of the n u c l e u s (a m o n o p o l e , b e c a u s e
2°= 1), whose e f f e c t on t h e e l e c t r o n s i s f u n d a m e n t a l in the study of e l e c t r o n i c
s t r u c t u r e [1] and d o e s not depend on the i s o t o p e c o n s i d e r e d . H e r e we a r e not
i n t e r e s t e d in it.
T h e following t e r m is the q u a d r u p o l e t e r m , of r a n k 2 (and of o r d e r 2 2 = 4,
whence t h e n a m e ) , which i s p r o p o r t i o n a l to l / r 3 a n d d e p e n d s on the d i r e c t i o n
of О Й (O c e n t r e of t h e n u c l e u s ) .
T h e n we find the h e x a d e c a p o l e t e r m (rank 4), e t c .
IAEA - S M R - 3 2 / 7 215
(b) Magnetic expansion
F o r the m a g n e t i c v e c t o r p o t e n t i a l , the l e a d i n g t e r m is due to t h e m a g n e t i c

dipole m o m e n t of the n u c l e u s ( r a n k 1), to which the n e u t r o n s c o n t r i b u t e —
as well as the protons, whose orbital magnetic m o m e n t s also contribute —
t h r o u g h t h e i r own spin m a g n e t i c m o m e n t .
T h e n we find the octupole t e r m ( r a n k 3), e t c .
(c) O r d e r s of m a g n i t u d e of h f s i n t e r a c t i o n s
T h e r e i s an a l t e r n a t i v e and e q u i v a l e n t way to d e s c r i b e the t o t a l e l e c t r o -

m a g n e t i c i n t e r a c t i o n b e t w e e n n u c l e u s and e l e c t r o n s . I n s t e a d of e x p a n d i n g t h e
f i e l d s of t h e n u c l e u s and s t u d y i n g t h e i r i n t e r a c t i o n s with m o v i n g e l e c t r o n s ,
we m a y obtain the e l e c t r i c and m a g n e t i c f i e l d s c r e a t e d by the e l e c t r o n s in
t h e v i c i n i t y of the c e n t r e of the n u c l e u s and c o m p u t e t h e i r e f f e c t s on t h e
n u c l e a r e l e c t r i c and m a g n e t i c m o m e n t s . In this way we s h a l l f i r s t d e r i v e
o r d e r s of m a g n i t u d e f o r h f s e n e r g y e f f e c t s , and l a t e r on w r i t e the h f s
Hamiltonian.
(a) Magnetic-dipole hfs
T h e e n e r g y a s s o c i a t e d with t h e m a g n e t i c dipole m o m e n t of, the n u c l e u s

and the m a g n e t i c induction В p r o d u c e d by t h e e l e c t r o n s at the n u c l e u s is -B.
В is a p u r e l y e l e c t r o n i c quantity. In t h e a t o m , t h e f u n d a m e n t a l q u a n t i t i e s
s u f f i c i e n t to d e f i n e a t o m i c u n i t s a r e h, m ( m a s s of t h e e l e c t r o n ) and e (and
e 0 o r /u0, t h e c o n s t a n t s which c h a r a c t e r i z e t h e C o u l o m b f o r c e ; e 0 /i 0 c 2 = 1). F o r
e x a m p l e t h e a t o m i c length unit i s t h e Bohr r a d i u s a = h 2 / m e 2 = 0.529 X10~ 8 c m
(a = 4тг e0 h 2 / m e 2 if r a t i o n a l i z e d ) . F o r the a t o m i c unit of В we obtain
M0 e 3 /(47r) 2 e 0 a 2 h = e 3 / ( 4 7 r e 0 f a 2 c 2 f i
Л is a p u r e l y n u c l e a r quantity. In t h e n u c l e u s , the f u n d a m e n t a l q u a n t i t i e s
s u f f i c i e n t t o d e f i n e n u c l e a r u n i t s a r e ft, M ( m a s s of the p r o t o n ) , f (the f e r m i ;
1 f e r m i = 1 0 " 1 3 c m ; the f e r m i i s of t h e o r d e r of m a g n i t u d e of the n u c l e a r
d i m e n s i o n s , and i s conveniently i n t r o d u c e d to c h a r a c t e r i z e t h e n u c l e a r s t r o n g
i n t e r a c t i o n ) and e , e 0 and ßQ f o r e l e c t r o m a g n e t i c p r o p e r t i e s , of c o u r s e . T h e n
we find e a s i l y that a l l n u c l e a r m a g n e t i c dipole m o m e n t s a r e of the o r d e r of
t h e quantity e f t / M . M o r e p r e c i s e l y , the n u c l e a r m a g n e t o n ß N (the unit f o r the
n u c l e a r m a g n e t i c m o m e n t s ) is t r a d i t i o n a l l y d e f i n e d a s e h / 2 M .
F i n a l l y , f o r the o r d e r of m a g n i t u d e of t h e m a g n e t i c - d i p o l e h f s e n e r g y ,
we obtain e 4 /2(47re 0 ) 2 a 2 c 2 M (check t h e d i m e n s i o n ! ) , which is a p p r o x i m a t e l y
0.4 X 10" 6 eV (3 mK in wave n u m b e r s ) . Note that t h i s r e s u l t . d o e s not depend
on t h e v a l u e of the d i m e n s i o n of the n u c l e i (the f e r m i ) , and a l s o not on ft.
(ß) E l e c t r i c - q u a d r u p o l e hfs
In the s a m e way the h f s e n e r g y due to t h e i n t e r a c t i o n of the n u c l e a r

e l e c t r i c q u a d r u p o l e m o m e n t ( d i m e n s i o n : c h a r g e X a r e a ) with t h e e l e c t r i c
f i e l d a r o u n d the n u c l e u s c a n b e c o m p u t e d . E v i d e n t l y it i s a m u l t i p l e of
H ( 1 0 f / a ) 2 w h e r e H, the H a r t r e e (1 H= 219 474 K), is t h e a t o m i c e n e r g y u n i t ;
h e r e we t a k e into account the f a c t that the unit f o r n u c l e a r q u a d r u p o l e m o m e n t s
is e X b a r n (often j u s t t h e n u m b e r of b a r n s i s given; 1 b a r n = 10" 24 c m 2 = (10f) 2 ).
216 BAUCHE
We d e d u c e the value 8 m K f o r t h e o r d e r of m a g n i t u d e of e l e c t r i c - q u a d r u p o l e
h f s e n e r g y , a v a l u e c l o s e to the r e s u l t f o r m a g n e t i c - d i p o l e hfs 1 .
In t h e following, we s h a l l l i m i t o u r s e l v e s to the study of t h e s e two c o n -
t r i b u t i o n s to the h f s . The n u c l e a r m u l t i p o l e s of h i g h e r r a n k a r e of m u c h
s m a l l e r i n f l u e n c e : f o r two s u c c e s s i v e e l e c t r i c (or m a g n e t i c ) m u l t i p o l e s , the
r a t i o of t h e i r e n e r g y c o n t r i b u t i o n s is of the o r d e r ( 1 0 f / a ) 2 . Studies of t h e
m a g n e t i c - o c t u p o l e e f f e c t s , f o r e x a m p l e , can b e found in the l i t e r a t u r e [ 2 ] .
To c o n c l u d e this p a r t , we m a y note that our e v a l u a t i o n of o r d e r s of
m a g n i t u d e s h o w s that it looks a c o i n c i d e n c e t h a t t h e e f f e c t s of m a g n e t i c -
dipole and e l e c t r i c - q u a d r u p o l e h f s h a v e a l m o s t the s a m e o r d e r of m a g n i t u d e .
2.1.2. E l e m e n t a r y t h e o r y of the m a g n e t i c - d i p o l e h f s : the s u b l e v e l s
U n t i l now we have not u s e d quantum t h e o r y , u n l e s s f o r the i n t r o d u c t i o n

of h to c a l c u l a t e the o r d e r s of m a g n i t u d e . We s h a l l now give the q u a n t u m
d e s c r i p t i o n of the m a g n e t i c - d i p o l e h f s .
(a) Hamiltonian : elementary part
To obtain a f o r m a l e x p r e s s i o n f o r the e n e r g y i n t e r a c t i o n , we f i r s t have

to find that f o r the m a g n e t i c field p r o d u c e d by the m o v i n g e l e c t r o n s at the
n u c l e u s . R e s t r i c t i n g the l o c a t i o n of an e l e c t r o n to t h e o u t s i d e of the n u c l e u s
we c o n s i d e r the following c a s e s :
The f i e l d H j p r o d u c e d by the moving c h a r g e - e defined by its p o s i t i o n ?
and i t s v e l o c i t y v :
.ri r Xv e r X pх
47гН.1 = - e —s— = m r-X 3
rd
The f i e l d H2 p r o d u c e d by the m a g n e t i c dipole m o m e n t jí of the e l e c t r o n ;

t h i s m o m e n t is
-2(3 s , w h e r e ß = e h / 2 m is the B o h r m a g n e t o n
(the a t o m i c unit f o r m a g n e t i c m o m e n t s ) and s is the s p i n of the e l e c t r o n ,

s is the a n g u l a r - m o m e n t u m v e c t o r o p e r a t o r of the e l e c t r o n , such that (?) 2
h a s a s t h e only e i g e n v a l u e s ( s + l ) with s = j and s z h a s the e i g e n v a l u e s ± j
( a c t u a l l y the spin a n g u l a r m o m e n t u m i s r a t h e r h s ) .
By c l a s s i c a l e l e c t r o m a g n e t i s m one obtains
л Û -= - _
4îrHo ±L +j. 3a * * ?)
—s"
Al MО
T h e n the c o r r e s p o n d i n g H a m i l t o n i a n ( i n t e r a c t i o n e n e r g y ) is
„ — ~Mo(Hi + Нг) - /им , w h e r e jîN is the m a g n e t i c dipole m o m e n t of the
n u c l e u s . Noting that r X p = hi, w h e r e Í i s t h e ( d i m e n s i o n l e s s ) o r b i t a l
1
Actually, the values of the nuclear quadmpole moments are close to 1 barn only in the second half of
the periodic table, and closer to 0 . 1 barn for Z smaller than 30.
IAEA-SMR-12/7 217
a n g u l a r m o m e n t u m of the e l e c t r o n , and d e l e t i n g 4т ( t r a d i t i o n a l l y , the

f o r m u l a s in q u a n t u m m e c h a n i c s a r e not r a t i o n a l i z e d ) , we c a n w r i t e f o r an
a t o m with s e v e r a l e l e c t r o n s
Now we t a k e into account the f a c t t h a t , f o r t h e n u c l e u s a s w e l l as f o r

the e l e c t r o n , the m a g n e t i c m o m e n t and the a n g u l a r m o m e n t u m a r e p r o p o r -
t i o n a l to e a c h o t h e r : Ды = ( / u N / I ) ß N t , w h e r e t is the ( d i m e n s i o n l e s s ) a n g u l a r
m o m e n t u m v e c t o r . In c o n t r a s t to the c a s e of the e l e c t r o n , the p r o p o r t i o n a l i t y
c o e f f i c i e n t c o n t a i n s ß N = e h / 2 M (see 2.1.1. (c), a) i n s t e a d of ß and M n /I is not
a s i m p l e n u m b e r , but h a s to be d e t e r m i n e d e x p e r i m e n t a l l y (for e x a m p l e
M ^ / I - 5.59 f o r t h e p r o t o n ) ; h o w e v e r , f r o m the g e n e r a l p r o p e r t i e s of a n g u l a r
m o m e n t u m o p e r a t o r s , we know that I, d e f i n e d by the f a c t that the e i g e n v a l u e
of the o p e r a t o r 11 | is 1(1+1), is e i t h e r an i n t e g e r o r a " h a l f - i n t e g e r "
( r a t h e r : h a l f - o d d ) n u m b e r (for e x a m p l e it is 1 f o r the n u c l e u s 2 H and 3 / 2
f o r 7 Li).
(b) Nuclear spins
Knowing that n u c l e i a r e built up of n u c l é o n s , i . e . p r o t o n s and n e u t r o n s ,

both with spin 1 / 2 , we know f r o m an e l e m e n t a r y r e s u l t on the coupling of
a n g u l a r m o m e n t a that n u c l e i with an e v e n n u m b e r of n u c l é o n s ( e v e n - e v e n and
odd-odd n u c l e i ) have an i n t e g r a l spin w h e r e a s an odd n u m b e r of n u c l é o n s
l e a d s to a h a l f - i n t e g r a l spin. M o r e o v e r , e x p e r i m e n t a l d e t e r m i n a t i o n s have
shown t h a t a l l s t a b l e e v e n - e v e n i s o t o p e s c o r r e s p o n d to the v a l u e 1= 0, w h e r e a s '
none of the few odd-odd s t a b l e n u c l e i d o e s .
As I = 0 l e a d s to juN = 0, we s e e that m o s t i s o t o p e s with an even m a s s
n u m b e r ( n a m e l y , t h e e v e n - e v e n i s o t o p e s ) give a t o m i c s p e c t r a l l i n e s without
any m a g n e t i c - d i p o l e s t r u c t u r e (we s h a l l s e e l a t e r that 1 = 0 p r e v e n t s the
e x i s t e n c e of any h f s at all).
(c) H a m i l t o n i a n : the F e r m i c o n t a c t t e r m
T h e f o r m u l a s we h a v e u s e d above f o r the i n t e r a c t i o n b e t w e e n the n u c l e a r

point m a g n e t i c m o m e n t and the m a g n e t i c f i e l d p r o d u c e d by the e l e c t r o n s a r e
not v a l i d if we allow t h e e l e c t r o n to e n t e r t h e n u c l e u s , a s it c a n . In t h i s c a s e ,
we must c o m p u t e the i n t e r a c t i o n b e t w e e n a point c h a r g e plus a point m a g n e t i c
m o m e n t (the e l e c t r o n ) and a s m a l l (although f i n i t e ) v o l u m e with a m a g n e t i s m
d i s t r i b u t i o n . C o n s i d e r i n g the l i m i t of t h i s i n t e r a c t i o n f o r a point n u c l e u s , we
obtain [3] the s o - c a l l e d F e r m i c o n t a c t t e r m , which m u s t b e added to ,
osd
to y i e l d t h e c o m p l e t e h f s m a g n e t i c - d i p o l e H a m i l t o n i a n
H„ - ^ { Z 6(î.)sJ-ï^ X-Î
where
218 BAUCHE
and w h e r e ô (?) is not a t r u e function but a " d i s t r i b u t i o n " , with the d e f i n i t i o n
J f*(r)6(r)f(?)dr= |f(ï)|2
space
f o r any a r b i t r a r y function f ( r )
(d) E l e m e n t a r y d e s c r i p t i o n of the a t o m i c wave f u n c t i o n
H m r e p r e s e n t s an i n t e r a c t i o n between n u c l e u s and e l e c t r o n s . T h e r e f o r e
it a c t s in a s p a c e of wave f u n c t i o n s d e s c r i b i n g both t h e s t a t e s of the n u c l e u s
and of t h e e l e c t r o n s . As we a r e i n t e r e s t e d g e n e r a l l y in one n u c l e a r l e v e l
(the g r o u n d l e v e l , m o s t o f t e n ) , we r e p r e s e n t it by k e t s of t h e type | I M j ) ,
w h e r e only I and M, (the p r o j e c t i o n of T on the z - a x i s ) a r e s p e c i f i e d . As in
t h e c a s e of the a t o m , we m a y often be i n t e r e s t e d in s e v e r a l a t o m i c l e v e l s .
M o r e o v e r we know [1] t h a t , in the a b s e n c e of e x t e r n a l f i e l d s 2 , e a c h a t o m i c
s t a t e is an e i g e n s t a t e of t h e o p e r a t o r [ j | f o r t h e eigenvalue J ( J + 1). We
w r i t e s u c h a s t a t e a s |a J M j ) , w h e r e a s p e c i f i e s the coupling (possibly i n t e r -
m e d i a t e [1] ), i. e. t h e way e l e c t r o n i c o r b i t a l and s p i n a n g u l a r m o m e n t a a r e
coupled to y i e l d J .
F i n a l l y , the wave f u n c t i o n of the c o m p l e t e s y s t e m ( e l e c t r o n s + n u c l e u s )
c a n be expanded on t h e b a s i s of the ket p r o d u c t s 3
\a J M )| I M , ) = I a J I Mj M,)
(e) Application of the p e r t u r b a t i o n m e t h o d
In the s p a c e of wave f u n c t i o n s just d e s c r i b e d , we m u s t c o n s i d e r t h e t o t a l

H a m i l t o n i a n H 0 + H m , w h e r e H0 is the e l e c t r o n i c H a m i l t o n i a n [ 1 ] . H 0 i s
d i a g o n a l , with e i g e n s t a t e s | a J I M j M j ) , c o r r e s p o n d i n g to t h e e n e r g i e s E a J ,
i n d e p e n d e n t of M j , I, and M j , d i f f e r i n g one f r o m the o t h e r by g e n e r a l l y at
l e a s t one h u n d r e d K a y s e r s in t h e i n t e r e s t i n g p a r t s of the a t o m i c s p e c t r a . So
the " s m a l l " H a m i l t o n i a n H m c a n be c o n s i d e r e d a s a p e r t u r b a t i o n . In the
f i r s t o r d e r of p e r t u r b a t i o n , we have t o d i a g o n a l i ž e t h e m a t r i x of H m on t h e
s u b s p a c e c o r r e s p o n d i n g to a given a j - l e v e l .
(f) Application of t h e W i g n e r - E c k a r t t h e o r e m
T h e f i r s t thing to do is to build up t h i s m a t r i x . Using t h e c o n d e n s e d

n o t a t i o n ( w i j M j ) = (a J I M . M j ) , we c a n w r i t e
2
In fact, the hfs phenomenon itself can be considered as the effect of a field "external" to the "atom" so
that, in principle, J is only an "almost good" quantum number.
3
If several nuclear levels are of interest and if their wave functions are known, one may label them as
iBIMj).
IAEA-SMR-12/7 219
(MJ M J | H ^ I M J ' M J ' ) = £ (MJMJIXÎ^M; M-)

q = x,y,z
= (Mj M Xq Mj M } (Mj M iq Mji m j>

Xq MJ*XM}* ' ' ' " " " "' ' '
= Y (M J Mj |X q |MJ' MJ ) (M,' MJ |l q I M j MJ' )
Now, b e c a u s e the o p e r a t o r X i s a v e c t o r a c t i n g in the e l e c t r o n i c s p a c e

like J , we c a n apply the W i g n e r - E c k a r t t h e o r e m and w r i t e
(Mj MJ I X q |Mj' Mj ) = A ^ (Mj Mj | J^ М/ Mj )
w h e r e A a J is i n d e p e n d e n t of M j , M j and Mj, and w h e r e J q (q = x , y , z ) is a

p r o j e c t i o n of J . C a l c u l a t i n g in the s a m e way a s above but b a c k w a r d s , we
d e r i v e the c l a s s i c a l Hamiltonian
H .M. = A a j I - J
Note : t h e r i g o r o u s d e r i v a t i o n j u s t given is o f t e n r e p l a c e d by the s h o r t e r

s e n t e n c e : " d u e to the p r e c e s s i o n of the a t o m a r o u n d J , the e x p e c t a t i o n v a l u e
of any v e c t o r in the s y s t e m is p r o p o r t i o n a l to J " .
If applied to the n u c l e u s , which is a s y s t e m of n u c l é o n s , it p r o v e s t h a t
i t s m a g n e t i c m o m e n t /JN i s p r o p o r t i o n a l to Г. A a J is c a l l e d the h y p e r f i n e
s t r u c t u r e c o n s t a n t of t h e l e v e l a J .
(g) Hfs s u b l e v e l s
With the new e x p r e s s i o n f o r H M (valid only in t h e s u b s p a c e of the

j a J I M j Mj ) s t a t e s ) we c a n i m m e d i a t e l y find the e n e r g i e s . We f i r s t go f r o m
t h e u n c o u p l e d s t a t e s | a J I M j M j ) t o the coupled s t a t e s | a J I F M p ) , by i n t r o -
d u c i n g the t o t a l a n g u l a r m o m e n t u m F = 3+1 T h e n we note that
2
H - ÄA (IÎ - M - |JF)
"M aJ о
T h e r e f o r e H M is d i a g o n a l on the b a s i s of the coupled s t a t e s , and i t s e i g e n -

values a r e
AW m t, J I F) = AaJ F(F+1)-I(I + D- J ( J + 1)
We s e e that e a c h a J - l e v e l of t h e e l e c t r o n i c s y s t e m is s p l i t up into a
n u m b e r of s u b l e v e l s c h a r a c t e r i z e d by the q u a n t u m n u m b e r F . T h i s n u m b e r
i s t h e s m a l l e r one of the n u m b e r s ( 2 J 4 1) and (21 + 1). M o r e o v e r a kind of
220 BAUCHE
L a n d é i n t e r v a l r u l e , w e l l known f o r t h e fine s t r u c t u r e e n e r g i e s [1]

a p p l i e s s o that
AWm(a J I F ) - A W m ( a J I F - l ) = AaJF
2.1.3. E l e m e n t a r y t h e o r y of the m a g n e t i c - d i p o l e h f s : t h e t r a n s i t i o n s
Having found the h f s s t r u c t u r e s of the l e v e l s , we c a n d e r i v e the s t r u c -

t u r e s of t h e l i n e s .
(a) S e l e c t i o n r u l e s f o r e l e c t r i c dipole t r a n s i t i o n s
Let u s c o n s i d e r an a t o m i c t r a n s i t i o n b e t w e e n two l e v e l s , a J and a ' J ' ,

which is " a l l o w e d " in the a b s e n c e of h f s . T h i s m e a n s that the line obeys t h e
s e l e c t i o n r u l e s f o r the type of r a d i a t i v e t r a n s i t i o n c a l l e d " e l e c t r i c dipole
t r a n s i t i o n " [ 1 ] , which s a y that t h e p a r i t i e s of the l e v e l s a r e d i f f e r e n t and
I J - J'| i 1 g j +ji.
Since the e l e c t r i c dipole t r a n s i t i o n o p e r a t o r E r . a c t s only in the e l e c t r o n i c
s p a c e , which is not i n f l u e n c e d by the p r e s e n c e of W s , t h e t r a n s i t i o n r e m a i n s
allowed a s a whole. T h e s e l e c t i o n r u l e on F is e x a c t l y analogous to that on
J : | F - F ' | S 1 Š F + F ' . It c a n b e kept in m i n d e a s i l y (and e v e n d e m o n s t r a t e d ,
in a way) by noting that an e l e c t r i c dipole photon c a r r i e s an a n g u l a r m o m e n -
t u m h., which i s t a k e n away f r o m the a t o m t h r o u g h the t r a n s i t i o n . T h e
p r i n c i p l e of c o n s e r v a t i o n of t o t a l angular m o m e n t u m f o r the s y s t e m (atom in
s u b l e v e l or J I F , a t o m in s u b l e v e l a 1 J 1 1 F ' + photon) i m m e d i a t e l y y i e l d s the
d e s i r e d t r i a n g u l a r condition.
— f • F =0
J = - J'= 1
F =1
• F . J . * -F = 1 J = 0 •
4 : - F=0
-F.J-* •F=J-1
IAEA-SMR-12/7 221
(b) Examples
(a) I s o t o p e with I = f
A l i n e s p l i t s into
3 components if J f J 1 (J and J ' f 0)

4 components if J = J' f j
3 components if J =J' = \
2 components if J or J ' = 0
(ß) One l e v e l with J = 0
N e c e s s a r i l y J ' = 1, and t h e l i n e
d o e s not s p l i t if I = 0
s p l i t s into 2 c o m p o n e n t s if I = \
s p l i t s i n t o 3 c o m p o n e n t s if I s 1
(с) Line intensities
The c o m p o n e n t i n t e n s i t i e s c a n b e c a l c u l a t e d in the s a m e way a s t h o s e

without h f s [ 1 ] , u s i n g the t e n s o r o p e r a t o r f o r m a l i s m . F o r a g i v e n a J - > a ' J '
t r a n s i t i o n , t h e y a r e a l l n u m e r i c a l m u l t i p l e s of one r e d u c e d m a t r i x e l e m e n t
s q u a r e d , n a m e l y | (q-jU? r t | | a ' J ' ) | 2 . T h e n u m e r i c a l c o e f f i c i e n t s h a v e b e e n
t a b u l a t e d f o r m a n y v a l u e s of J and I [ 4 , 5 ] .
2.1.4. T h e o r y of the e l e c t r i c - q u a d r u p o l e h f s
T h e m a g n e t i c - d i p o l e h f s w a s s t u d i e d above without t h e u s e of t e n s o r
o p e r a t o r m e t h o d s with t h e only a i m of an e x p l i c i t c o m p u t a t i o n of t h e c o m p o n e n t
i n t e n s i t i e s . F o r the e l e c t r i c - q u a d r u p o l e p a r t of t h e h f s , t h e r e s u l t s w e r e
o b t a i n e d by C a s i m i r (1936) at t h e end of a long w o r k . T h e y c a n now b e
r e p r o d u c e d v e r y e a s i l y by u s e of R a c a h ' s m e t h o d s .
(a) The H a m i l t o n i a n
In t e n s o r - o p e r a t o r f o r m , t h e m a g n e t i c - d i p o l e H a m i l t o n i a n i s w r i t t e n a s
a scalar product
Hm = (X(1)-I(1))
To obtain t h e e l e c t r i c - q u a d r u p o l e H a m i l t o n i a n , t h e t o t a l i n t e r a c t i o n e n e r g y
b e t w e e n t h e e l e c t r o n s (with t h e i r p o s i t i o n s d e f i n e d by v e c t o r s l i k e r ; ) and t h e
в
p r o t o n s ( p o s i t i o n s : Rj) i s w r i t t e n a s
» • Zт^ ii.i j кi , - R-
222 BAUCHE
T h e f r a c t i o n c a n b e expanded a s
w h e r e the o p e r a t o r C(k)
c o r r e s p o n d s to e l e c t r o n a n g u l a r c o - o r d i n a t e s and
to n u c l é o n a n g u l a r c o - o r d i n a t e s . S e l e c t i n g t h e p a r t of the e x p a n s i o n
with k= 2, and applying the W i g n e r - E c k a r t t h e o r e m to the n u c l e a r p a r t , we
obtain t h e e l e c t r i c - q u a d r u p o l e h f s H a m i l t o n i a n
Hq = ( Y ( 2 ) . K t 2 ) )
where
(2) e 2 Q Y Cj(2>
(electronic operator)
1(21-1) Л г »
and
K (2) = J l (I(Dl(l)}W (nuclear operator)
Q i s t h e e l e c t r i c q u a d r u p o l e m o m e n t of the n u c l e u s . Hq is not d e f i n e d
f o r 1 = 0 and i , in which c a s e t h e r e is no h f s q u a d r u p o l e i n t e r a c t i o n .
Note on k ' 2 ^ : in the e x p r e s s i o n f o r K^ 2 ', n/ 3 / 2 is a t r a d i t i o n a l f a c t o r ; the

operator (I^'l ^ is the s i m p l e s t t e n s o r o p e r a t o r of r a n k 2 built up f r o m
j(i) (j(l) b e i n g t h e only n u c l e a r o p e r a t o r w h o s e e i g e n v a l u e s a r e known in our
s i m p l e q u a n t u m d e s c r i p t i o n of t h e n u c l e u s ) .
(b) Energies
We e a s i l y c a l c u l a t e the d i a g o n a l m a t r i x e l e m e n t s of H q [1]:
(a J I F M p I (Y f2> "K ( 2 ) )\a J I F ' M ^ )
= (-1) , + I + F б (F, F ' ) 6(Мр, Мр ) (« J||Y ( 2 ' M ( I II К ( 2 ) | | I)
T h i s r e s u l t p r o v e s t h a t the coupled s t a t e s |a J I F M f ) , which a r e t h e

e i g e n s t a t e s of H m in t h e s u b s p a c e c o r r e s p o n d i n g t o t h e l e v e l a J , a r e a l s o
t h e e i g e n s t a t e s of Hq in the s a m e s u b s p a c e . T h e d e p e n d e n c e of the e n e r g y
A W q ( a J I F ) on F i s given by the f a c t o r
T h e f o r m a l e x p r e s s i o n of t h e 6 i - s y m b o l c a n b e found in the l i t e r a t u r e ([6] p. 132).

The reduced m a t r i x
e l e m e n t (I||K ( 2 ) ||I) c a n be c a l c u l a t e d by m e a n s of a f o r m u l a
f o r two coupled t e n s o r o p e r a t o r s acting on the s a m e s y s t e m ([6] p. 109).
IAEA-SMR-12/7 223
(с) The C a s i m i r f o r m u l a
F i n a l l y , t h e h f s e n e r g y f o r a s u b l e v e l a J I F in the p r e s e n c e of both
m a g n e t i c - d i p o l e and e l e c t r i c - q u a d r u p o l e e f f e c t s i s given by t h e t r a d i t i o n a l
Casimir formula
3K(K + 1) - 41(1 + 1) J ( J + 1 )
A Wa J I F j A a j K + B aJ
81 (21 - 1) J (2 J - 1)
w h e r e К = F<F + 1 ) - 1(1 + 1 ) - J{ J + 1 ) and the h y p e r f i n e c o n s t a n t s of the l e v e l

a J are
A a J = ( a j II X(1)||or J) [J ( J + 1) ( 2 J + 1)]~* (I, J ž •§)
and
B a J = ( o j | | y ' 2 ' I I a j ) 21(21-1 ) [ J ( 2 J - 1 ) / ( J + l ) ( 2 J + l ) ( 2 J + 3 ( I , J ž l )
T h i s f o r m u l a s h o w s c l e a r l y t h a t , in the f i r s t o r d e r of p e r t u r b a t i o n , two
" p a r a m e t e r s " , A and B, a r e s u f f i c i e n t to i n t e r p r e t t h e h f s s t r u c t u r e of a
l e v e l , l i m i t e d to the m a g n e t i c - d i p o l e and e l e c t r i c - q u a d r u p o l e c o n t r i b u t i o n s .
M o r e i m p r e s s i v e is the c o n c l u s i o n that f o u r p a r a m e t e r s a r e s u f f i c i e n t to
i n t e r p r e t t h e h f s s t r u c t u r e of a l i n e , w h a t e v e r the n u m b e r of c o m p o n e n t s .
T h i s c o n c l u s i o n and the C a s i m i r f o r m u l a can b e u s e d to " r e s o l v e " n u m e r i c a l l y
a h f s s t r u c t u r e with u n r e s o l v e d c o m p o n e n t s , if t h e p r o f i l e of an i s o l a t e d
c o m p o n e n t is a c c e s s i b l e .
When t h e C a s i m i r f o r m u l a f a i l s to i n t e r p r e t t h e p o s i t i o n s of t h e h f s
c o m p o n e n t s , this m a y b e due to
(a) e r r o r s in the i d e n t i f i c a t i o n of the c o m p o n e n t s ; f o r t h i s i d e n t i f i c a t i o n , t h e

i n t e n s i t y r a t i o s ( s e e 2.1.3. c) a r e an e s s e n t i a l help;
(b) e n e r g y c o n t r i b u t i o n s due to the s e c o n d o r d e r of p e r t u r b a t i o n of t h e
H a m i l t o n i a n H m + H q , in the c a s e w h e r e n e i g h b o u r i n g J - l e v e l s a r e r e l a -
tively c l o s e to one a n o t h e r ;
(c) e n e r g y c o n t r i b u t i o n s due to m u l t i p o l a r h f s e f f e c t s of h i g h e r r a n k .
2.2. I n t e r p r e t a t i o n of t h e h f s c o n s t a n t s of t h e l e v e l s
A f t e r h a v i n g d e t e r m i n e d t h e c o n s t a n t s AaJ and B a J f o r one o r s e v e r a l

l e v e l s , an e x p e r i m e n t a l i s t is i n t e r e s t e d in t h e i r i n t e r p r e t a t i o n .
2.2,1. Hfs c o n s t a n t s of the e l e c t r o n s
(a) M o r e d e t a i l e d d e s c r i p t i o n of the a t o m i c wave f u n c t i o n
Now we h a v e to g a t h e r m o r e i n f o r m a t i o n on an i n t e r e s t i n g l e v e l t h a n
j u s t i t s e n e r g y and J - v a l u e . M o r e p r e c i s e l y , we a r e i n t e r e s t e d to know both
t h e e l e c t r o n i c c o n f i g u r a t i o n t o which the l e v e l e s s e n t i a l l y b e l o n g s and the
coupling c o r r e s p o n d i n g to this l e v e l [ 1 ] .
224 BAUCHE
In g e n e r a l , t h i s i n f o r m a t i o n i s o b t a i n e d t h r o u g h a c o n s i d e r a t i o n of t h e
l e v e l e n e r g i e s , w h i c h i s t h e e a s i e r t h e m o r e l e v e l s of t h e c o n s i d e r e d p a r t of
the e n e r g y s p e c t r u m a r e known. I n p r i n c i p l e , coupling i s a l w a y s i n t e r m e d i a t e [1],
but s o m e t i m e s a p u r e and s i m p l e c o u p l i n g (LS, j j , etc. ) m a y be
considered a satisfactory approximation.
(b) T h e p r i n c i p l e of the c o m p u t a t i o n f o r an a l k a l i
T h e s p e c t r a of t h e a l k a l i s m a y b e c o n s i d e r e d , in a n e x c e l l e n t a p p r o x i -
m a t i o n , as o n e - e l e c t r o n s p e c t r a . This m e a n s that all atomic configurations
w h e r e one e l e c t r o n of the c o m p l e t e s u b s h e l l s (the " c o r e " ) h a s b e e n e x c i t e d ,
l i e v e r y h i g h a b o v e t h e c o n f i g u r a t i o n s [ c o r e + one n í e l e c t r o n ] . Consequently
a low l e v e l of an a l k a l i c a n b e d e n o t e d a s [ c o r e + n i j ] .
W e now c a l c u l a t e the h f s c o n s t a n t A f o r t h i s l e v e l , f r o m
i i
with
Г; (Sj T j )
N.1 = 1I. -1 s. + 3 • 1 ^2 11
F i r s t , r e c o u p l i n g of t h e t e n s o r o p e r a t o r s s h o w s t h a t
. ^+3 M ç i i ^ , - ^ïï{S;i,c;2)}(1) (show it -, )
O b v i o u s l y t h e a t o m i c c o r e ( c o u p l e d to J = 0) d o e s not c o n t r i b u t e to the
h f s s i n c e t h e r e d u c e d m a t r i x e l e m e n t of X ( 1 ) ( s e e 2 . 1 . 4 . c) i s z e r o f o r J = 0
s y s t e m s . T h e r e f o r e we j u s t c a l c u l a t e the q u a n t i t y
(níej|| Д ( * ( 1 ) - Л о { 3 № с ^ j ^ + fLôfr^llnisj)
H e r e w e u s e t h e c l a s s i c a l f o r m u l a s f o r t h e m a t r i x e l e m e n t s of c o u p l e d
t e n s o r o p e r a t o r s a n d / o r coupled s y s t e m s [1].
(c) Hfs c o n s t a n t s of the e l e c t r o n s
It i s e v i d e n t t h a t , at the end of t h i s c a l c u l a t i o n , we a r e l e f t w i t h t h e
r e d u c e d m a t r i x e l e m e n t s of ( l / r 3 ) i ( 1 ) , ( l / r 3 ) C ( 2 ) and 6 ( r ) s ( 1 ) . By m e a n s of
t h e W i g n e r - E c k a r t t h e o r e m , t h e y a r e e a s i l y r e l a t e d t o the m a t r i x e l e m e n t s
t h e m s e l v e s of, s a y , the q= 0 c o m p o n e n t s of the t e n s o r o p e r a t o r s . In t h e s e
e l e m e n t s a p p e a r the i n t e g r a l s
DO
< Г = |u
' \ I n*(r)|2 ^ r 2 d r and
/ 1 Ф П*Т/ ? >| 2 ё (?><1т
0 space
IAEA-SMR-12/7 225
1
where m ^(r) is the s p a t i a l p a r t of t h e o n e - e l e c t r o n wave f u n c t i o n ï^ tsm m
1 s
and u,^ (r) is the r a d i a l p a r t .
The f i r s t i n t e g r a l , h o w e v e r , is u s e f u l only if the r e d u c e d m a t r i x e l e m e n t s
of Je*1) and C ( 2 )
a r e n o n - z e r o , which is the c a s e only f o r l фО. M o r e o v e r , the
s e c o n d i n t e g r a l h a s the v a l u e of lu^ ( 0 ) | 2 , which is n o n - z e r o only if i = 0 .
We c o n c l u d e that the o r b i t a l p a r t ( i ( 1 ) ) and t h e s p i n - d i p o l e p a r t ({s (1 'c (2) } (1) )
of H m c o n t r i b u t e to the h f s of a l l e l e c t r o n s e x c e p t the s - e l e c t i o n s (11=0), and
t h a t the F e r m i - c o n t a c t p a r t (s (1) ) c o n t r i b u t e s only to the h f s of s - e l e c t r o n s .
T h e h f s c o n s t a n t s A f o r a l k a l i l e v e l s (and m o r e g e n e r a l l y f o r e a c h l e v e l of an
a r b i t r a r y p u r e c o n f i g u r a t i o n of an a r b i t r a r y s p e c t r u m ) can be e x p r e s s e d in
t e r m s of the h f s - c o n s t a n t s of the e l e c t r o n s
and
2
ans = 3 I
| nsv(0)|
1u
'1
Note: f o r e x p l i c i t c a l c u l a t i o n s , a t i m e - s a v i n g n u m e r i c a l help is the following:

if the v a l u e of a ^ is to be obtained in m K , and the v a l u e of ^ r " 3 ^ is given in
a t o m i c u n i t s (the a t o m i c unit f o r this quantity is 1 / a 3 ) , then 2ß ßN - 3 . 1 8 2
(check t h i s r e s u l t ! ).
In the s a m e way a s above, h f s e l e c t r o n i c c o n s t a n t s c a n be defined f o r
the e l e c t r i c - q u a d r u p o l e e f f e c t :
bni = e 2 Q < r - 3 > n { (£?0)
(d) E x a m p l e s of r e s u l t s
(a) L e v e l ni j in an a l k a l i
A nsi,
R - Ед-1) b a 41)
nij (2 j + 2 ) n£ 4 rz)
(ß) C o n f i g u r a t i o n sp
M a t r i x of a.
Ü.
C o e f f i c i e n t 4 of a s = ( % P » S L j j l ^ H , l P a S ' L ' J )
( f f j | | j II a J)
4
Taking into account the fact that, for one-particle operators and matrix elements between states of one
and the same configuration, the antisymmetry problem, when solved (see [1]) yields this simple result.
226 BAUCHE
T h e n u m e r a t o r of this f r a c t i o n c a n b e w r i t t e n [1] as
(-ds+l+j+1[J; l ^ K b ,
щ © »
and the new r e d u c e d m a t r i x e l e m e n t r e a d s
Moreover
( a j | | J ( 1 ) I <*J) = -J J ( J + 1 ) ( 2 J + 1)
So we have obtained the g e n e r a l f o r m u l a s which give u s a l l e l e m e n t s of
the m a t r i x of the c o e f f i c i e n t s of a s . A f t e r having applied it n u m e r i c a l l y
(do i t ! ) , we can c h e c k the v a l u e s of t h e d i a g o n a l e l e m e n t s in the following way:
We f i r s t note that
( s p S L j | | S s ( 1 ) | | s p S L J ) = (s p S L j | | Sp 1 '||s p SLJ)
b e c a u s e both e l e c t r o n s p i n s e n t e r the coupling in the s a m e way.

T h e n we know t h a t , in t h e study of t h e Z e e m a n e f f e c t in LS coupling [ 1 ] ,
the L a n d é f a c t o r is given by
( a S L j | | S (1) IIa S L J ) = J (J + 1 ) + S(S + 1 ) - L(L + 1 )

g SU = + (1) = + 2J
* (.SLJ||J ||.SLJ) <J+1>
Since S (1) = S ^ ' + S p 4 , we deduce i m m e d i a t e l y
(s p S L J H Ss 1 '|]sp S L J ) _ 1 - J ( J + 1 ) + S(S + 1 ) - L ( L + 1)
(*J||J(1)|M 4 J (J + 1 )
// 3
P, 'p. g ^ g t ^ f
1 1 g(4 )= 1
и 2Í2
1
0
2УУ
1
Д
IAEA-SMR-12/7 227
M a t r i x of a p
In the m a t r i x of a p e a c h e l e m e n t is the s u m of two q u a n t i t i e s , one

c o r r e s p o n d i n g to the o r b i t a l p a r t and the o t h e r to t h e s p i n - d i p o l e p a r t .
T o obtain the o r b i t a l p a r t we m u s t c a l c u l a t e
( s p S L J [I L ( 1 ) | | s p S ' L ' J )
( « J II J ( 1 ) | | A J )
b e c a u s e the s - e l e c t r o n g i v e s no c o n t r i b u t i o n to the t o t a l IL.

We obtain
( - l ) S ' + L ' + , + 1 t J ] - j ^ g ^ . j - 6(S,S')(ßL|| L(1)||ß'L')

However,
(ßL II L ||ß ' L ' ) = 5 (ß,ß ')ô(L, L') N/L(L + 1 ) ( 2 L + 1)
The m a t r i x is d i a g o n a l . T h e r e is a g a i n an e a s i e r way to c a l c u l a t e it in the

s a m e way a s above.
C o e f f i c i e n t of a p = 2 - g a J
3p
, 'P,
1
2 0
'p, 0 1
1
2
Spin-dipole part 4
'P| 'p,
1 (compute the o t h e r
10 elements ! )
(compute a l s o the
P
2 c o e f f i c i e n t s of bp ! )
228 BAUCHE
(e) D e t e r m i n a t i o n of t h e hfs c o n s t a n t s
T h e work we have done f o r t h e s e few c a s e s c a n b e done f o r any l e v e l of

any c o n f i g u r a t i o n in any coupling. Of c o u r s e , in a l a r g e c o n f i g u r a t i o n in
i n t e r m e d i a t e coupling, t h e r e a r e lots of m a t r i x e l e m e n t s to c o m p u t e , g e n e r a l l y
on an L S - c o u p l i n g b a s i s ; i n d e e d , if
|aJ)=
X lßSLJ)
BSL
then
(a j | | Op II a J) = Y (ßSLj||Op|| ß'S'L'J)x«su x « ^
BSL
ß'S'L'
f o r any a r b i t r a r y o p e r a t o r O p . 5
When we h a v e obtained the e x p r e s s i o n of A (or B) f o r the i n t e r e s t i n g
l e v e l ( s ) , in t e r m s of the h f s c o n s t a n t s f o r t h e e l e c t r o n s , the work m a y
p r o c e e d in two d i f f e r e n t w a y s :
(a) If s e v e r a l m e a s u r e m e n t s a r e a v a i l a b l e f o r l e v e l s of the s a m e
c o n f i g u r a t i o n , they m a y be n u m e r o u s enough to allow the d e t e r m i n a t i o n of
the e l e c t r o n i c h f s c o n s t a n t s , with the help of t h e " p a r a m e t r i c " m e t h o d : one
s o l v e s , by l e a s t - s q u a r e s , the s e t of e q u a t i o n s
n i
A , = Y x a „
oíjJí i nC
ní
w h e r e the A a . j a r e e x p e r i m e n t a l v a l u e s (the e q u a t i o n s a r e not c o m p a t i b l e ,

but m u s t be a l m o s t c o m p a t i b l e ; s e e [1] ).'
(b) An a b - i n i t i o m e t h o d m a y be u s e d to c o m p u t e d i r e c t l y the v a l u e s of
the electronic hfs constants ( H a r t r e e - F o c k method, L a y z e r method, etc. ;
s e e [1]), and then the l e v e l h f s c o n s t a n t s , with m o r e o r l e s s (but e s s e n t i a l l y
unknownj) a c c u r a c y . E x c e p t f o r s o m e r e c e n t , e f f e c t i v e but c u m b e r s o m e ,
m e t h o d s (those of t h e B r u e c k n e r - G o l d s t o n e t y p e , f o r e x a m p l e ) , t h e s e
a b - i n i t i o m e t h o d s give often no b e t t e r r e s u l t s than t h e old, f a m o u s s e m i -
c l a s s i c a l f o r m u l a s like the G o u d s m i t - F e r m i - S e g r é f o r m u l a [ 5 ] .
2.3. Results — Refinements
2.3.1. Results
So f a r we have d e f i n e d the g e n e r a l p r o c e d u r e f o r studying t h e o r e t i c a l l y

the h f s l e v e l c o n s t a n t s m e a s u r e d ; now let u s c o n s i d e r the types of r e s u l t s
obtained in t h i s way.
We obtained t h e ( m o r e o r l e s s a c c u r a t e ) v a l u e s of m a n y n u c l e a r m a g n e t i c -
dipole and e l e c t r i c - q u a d r u p o l e m o m e n t s ; t h e p r e s e n t s i t u a t i o n , h o w e v e r , is
s o m e w h a t d i f f e r e n t (for m a g n e t i c m o m e n t s only), b e c a u s e m a n y m a g n e t i c
5
There exist computer programs to compute such large numbers of matrix elements!
IAEA-SMR-12/7 229
m o m e n t s h a v e b e e n d e t e r m i n e d d i r e c t l y ( f o r e x a m p l e t h r o u g h t h e s t u d y of t h e
Z e e m a n e f f e c t in s t r o n g f i e l d s ) .
We a l s o found an " i n t e r p r e t a t i o n " of m a n y m e a s u r e m e n t s , i . e . m a n y
A - v a l u e s of l e v e l s in t h e s a m e c o n f i g u r a t i o n m a y b e " i n t e r p r e t e d " by a v e r y
s m a l l n u m b e r of p a r a m e t e r s , w h i c h p r o v e s t h e c o h e r e n c e of a l l t h e s e
measurements.
F i n a l l y , new p r o b l e m s of a t o m i c s t r u c t u r e a r o s e , i. e. c a s e s w h e r e t h e
m e t h o d s o u t l i n e d a b o v e h a v e f a i l e d . We now s t u d y s u c h c a s e s .
2.3.2. Configuration interaction
So f a r we h a v e s u p p o s e d t h a t t h e l e v e l s s t u d i e d b e l o n g to a p u r e c o n f i g u -
r a t i o n . But it f r e q u e n t l y h a p p e n s t h a t the f i r s t o r d e r of p e r t u r b a t i o n t h e o r y ,
applied to the " p e r t u r b i n g Hamiltonian" [1].
( e s s e n t i a l l y V) — e2 + V
in _ OTbit ), is not a s a t i s f a c t o r y a p p r o x i m a t i o n .
•T1- r i j
i>]
(a) M i x i n g of n e i g h b o u r i n g c o n f i g u r a t i o n s
In s o m e c a s e s two c o n f i g u r a t i o n s a p p e a r in the s p e c t r u m a l m o s t at the

same energy; o f t e n t h e y s i m p l y e x t e n d o v e r s u c h a l a r g e r a n g e of e n e r g y
t h a t t h e y o v e r l a p s t r o n g l y . U s u a l l y , t h e two c o n f i g u r a t i o n s a r e t h e r e f o r e
taken together as a b a s i s for diagonalizing the p e r t u r b i n g Hamiltonian. T h e
e i g e n s t a t e s b e c o m e a m i x t u r e of k e t s b e l o n g i n g to two c o n f i g u r a t i o n s . It i s
e a s y t o p r o v e t h a t the e x p r e s s i o n s f o r the c o r r e s p o n d i n g A - f a c t o r s c o n t a i n
s u p p l e m e n t a r y ( o f f - d i a g o n a l ) e l e c t r o n i c h f s c o n s t a n t s , with i n t e g r a l s of t h e t y p e
OO
(b) Other difficulties
In a s e r i e s of o t h e r c a s e s , a s a t i s f a c t o r y i n t e r p r e t a t i o n of A - c o n s t a n t s
c a n n o t b e o b t a i n e d b y t h e a p p l i c a t i o n of t h e m e t h o d o u t l i n e d a b o v e , a l t h o u g h
n o n e a r b y c o n f i g u r a t i o n c a n be s e e n w h i c h would c a u s e t h i s t r o u b l e . D i f f i c u l -
t i e s m a y i n d e e d a p p e a r at two d i f f e r e n t s t a g e s .
(a) T h e f o r m a l e x p r e s s i o n s of t h e c o n s t a n t s A m a y b e s e e n to d i s a g r e e
w i t h e x p e r i m e n t , s u c h a s in t h e c a s e of L i I l s 2 2 p :
A ( 2 P i / 2 ) = 46.17 ± 0.35 MHz

2 (experimental values for 7Li)
A( P ) = - 3 . 0 7 ± 0 . 1 3 MHz
But o u r f o r m u l a ( 2 . 2 . 1 . (d)) p r e d i c t s A ( P 1 / 2 ) / A ( P 3 / 2 ) = + 5! H e r e we s p e a k of a
" p a r a m e t r i c " difficulty.
230 BAUCHE
2 (energy in К)
L i - I low l e v e l s : I s 2s
О
l s 2 2 p J = 1 /2 14 903.66
J = 3/2 14 904.00
ls23s 27 206
ls23p J = 1 /2, 30 925

3/2
Obviously no o t h e r c o n f i g u r a t i o n is " c l o s e " to the i n t e r e s t i n g l e v e l s .
(ß) T h e " e x p e r i m e n t a l " v a l u e s f o r the e l e c t r o n i c h f s c o n s t a n t s m a y be

of the w r o n g o r d e r of m a g n i t u d e , c o m p a r e d to the a b - i n i t i o e v a l u a t i o n s ,
e. g. in the c a s e of Mn III 3 d 5 6 S 5 / 2 .
E P R m e a s u r e m e n t s with Mn s a l t s y i e l d e d a r a t h e r l a r g e h y p e r f i n e
c o n s t a n t A f o r the g r o u n d - s t a t e l e v e l 3d 5 6 S 5 ^ 2 . Now t h i s l e v e l , c o r r e s p o n d i n g
to L = 0 and c o n t a i n i n g no u n p a i r e d s - e l e c t r o n , should have the hfs c o n s t a n t s
A= B= 0. A c t u a l l y , LS coupling is not e x a c t l y f u l f i l l e d , but t h e v e r y s m a l l
m i x i n g of t h i s l e v e l with t h e o t h e r 3d s J = 5 / 2 l e v e l s (through i n t e r m e d i a t e
coupling) cannot e x p l a i n the A - v a l u e m e a s u r e d , u n l e s s t h e a d - c o n s t a n t is
given an u n r e a s o n a b l y l a r g e v a l u e ( s o t h i s c a n b e c a l l e d an " a b - i n i t i o " difficulty).
(c) Spin-core-polarization
T h e p r o b l e m of M n " and o t h e r 3d N c o n f i g u r a t i o n s is c o n s i d e r e d a s
solved by A b r a g a m , Horowitz and P r y c e [7] in 1955, who i n t r o d u c e d the
notion of " c o r e p o l a r i z a t i o n " . T h i s p h e n o m e n o n , a c o r r e c t i o n to the s i n g l e -
c o n f i g u r a t i o n m o d e l , c a n be d e s c r i b e d in t h r e e w a y s :
( a ) it c a n be s e e n a s t h e r e s u l t of the m i x i n g of the c o n f i g u r a t i o n u n d e r
study with e x c i t e d c o n f i g u r a t i o n s c o n t a i n i n g u n p a i r e d s - e l e c t r o n s . E x a m p l e :
m i x i n g of l s 2 2 s 2 . . . 3d 5 ®S with ( I s n s ) 3 S 2 s 2 . . 3d 5 indeed the F e r m i c o n t a c t
H a m i l t o n i a n g i v e s an o f f - d i a g o n a l e l e m e n t b e t w e e n t h e s e two t e r m s , and a l s o
a d i a g o n a l e l e m e n t f o r t h e e x c i t e d t e r m . Of c o u r s e m i x i n g is v e r y s m a l l
( b e c a u s e t h e e x c i t e d t e r m i s s o high), but this is c o m p e n s a t e d by the e x t r e m e l y
high v a l u e of Uj s (0) s o that an a p p r e c i a b l e e f f e c t r e s u l t s . Note that t h e
e x c i t a t i o n of a n o n - s - e l e c t r o n would give no e f f e c t , b e c a u s e L= 0.
(ß) It c a n b e r e g a r d e d a l s o in a n o t h e r way which we s h a l l d e s c r i b e with

the h e l p of the s i m p l e r e x a m p l e of L i I 1 ^ 2 p . C o n s i d e r t h e s t a t e M L = 1,
M s = + •§•. T h e c o r r e s p o n d i n g wave f u n c t i o n c o n t a i n s two l s - e l e c t r o n s with
the spin projections and - i and one 2 p - e l e c t r o n with spin p r o j e c t i o n + §.
If we i n d i v i d u a l i z e the e l e c t r o n s (although t h e t o t a l f u n c t i o n m u s t b e a n t i -
s y m m e t r i c ! ), we c a n s a y that t h e r e p u l s i o n b e t w e e n the I s and the 2p is
s m a l l e r than b e t w e e n I s and 2p; indeed, in the f i r s t c a s e t h e r e a p p e a r s in
t h e i n t e r a c t i o n e n e r g y an e x c h a n g e S l a t e r i n t e g r a l ( G 1 ( l s , 2 p ) ) with a n e g a t i v e
s i g n , u n l i k e the s e c o n d c a s e . So if we allow the two l s - e l e c t r o n s to c o r r e s -
pond to d i f f e r e n t r a d i a l f u n c t i o n s , a wave f u n c t i o n c a n b e found which is
IAEA-SMR-12/7 231
c e r t a i n l y c l o s e r to the t r u e wave f u n c t i o n than the c e n t r a l - m o d e l wave

function. The s p i n - u n r e s t r i c t e d H a r t r e e - F o c k method has been derived
along t h e s e l i n e s .
C o n s i d e r e d in the s a m e way a s L i I l s ? 2 p (M L = 1 M g = + i ) , the s t a t e
Mn + + I s 2 . . . 3d 5 6 S (ML =0 M s = 5 / 2 ) p o s s e s s e s five 3 d - e l e c t r o n s with m s = +
which i n t e r a c t in a d i f f e r e n t m a n n e r with a l l the and - \ s - e l e c t r o n s .
(7) If we want to s t i c k to the p a r a m e t r i c m e t h o d , we can u s e a r e s u l t of

Judd [9] f o r t h e n i N c o n f i g u r a t i o n s : t h e A ^ - c o n s t a n t of any l e v e l of a c o n -
f i g u r a t i o n i N can b e c o r r e c t e d f o r t h e c o r e - p o l a r i z a t i o n e f f e c t by j u s t adding
to it t h e quantity c f g ^ j - l ) , w h e r e с is a new p a r a m e t e r to b e o p t i m i z e d .
(d) Far-configuration interaction; general case
R e c e n t l y (1965) t h e f a r - c o n f i g u r a t i o n i n t e r a c t i o n p h e n o m e n o n w a s c l e a r l y
put into e v i d e n c e a l s o f o r the SL - d e p e n d e n t m a g n e t i c h f s ( t e r m s in and
{s ( 1 ) C (2) }), f r o m e x p e r i m e n t s by H a r v e y [8] on t h e oxygen ( O) ground t e r m
2 p 4 3 P . V e r y a c c u r a t e m e a s u r e m e n t s allowed H a r v e y to d e t e r m i n e f o u r h f s
A - v a l u e s (A( 3 Pj), A( 3 P 2 ) and two o f f - d i a g o n a l A - c o n s t a n t s ) . T h e n he t r i e d to
i n t e r p r e t t h e m with t h e p a r a m e t e r s a 2 p and с (see the above p a r a g r a p h ) ; t h i s
t w o - p a r a m e t e r fit showed l a r g e d i s c r e p a n c i e s with the e x p e r i m e n t a l v a l u e s .
He then s u p p o s e d that the a ç p - p a r a m e t e r s m a y be d i f f e r e n t f o r t h e i d ) and t h e
2
{S(1)C< >}(1) h f s p a r t s . F o r this t h r e e - p a r a m e t e r fit a 2 p (sC), and
a 2 p (s) - a new notation f o r c), the i n t e r p r e t a t i o n of the f o u r e x p e r i m e n t a l
values becomes excellent.
Judd [9] g a v e a t h e o r e t i c a l s u p p o r t to t h i s new p a r a m e t r i c p r o c e d u r e .
He showed t h a t , in an L S - t e r m of , t h e s e c o n d - o r d e r c r o s s e d e f f e c t s of the
e l e c t r o s t a t i c C o u l o m b r e p u l s i o n and of t h e h f s m a g n e t i c (and e l e c t r i c )
H a m i l t o n i a n can be t a k e n into a c c o u n t , k e e p i n g t h e LS wave f u n c t i o n s c h e m e ,
u n d e r the a s s u m p t i o n that the v a l u e s of ^ r " 3 ) ^ m a y b e d i f f e r e n t f o r the
and t h e {s ( 1 ) C ( 2 '} ( 1 ) (and t h e C (2) ) p a r t s . T h i s is an a p p l i c a t i o n of t h e s o -
c a l l e d m e t h o d of e f f e c t i v e o p e r a t o r s , which i s widely u s e d in o t h e r f i e l d s of
atomic physics.
Note: J r ^ f a c t , we h a v e e n c o u n t e r e d above o t h e r e f f e c t i v e o p e r a t o r s : A a j l - J
and с S-1, the o p e r a t o r which b r i n g s the a d d i t i v e c o n t r i b u t i o n c f g ^ - l ) to
A ^ i n JP n . A g e n e r a l p r o p e r t y of e f f e c t i v e o p e r a t o r s is t h a t t h e v a l i d i t y of
e a c h one is r e s t r i c t e d to a l i m i t e d wave f u n c t i o n s p a c e .
(e) The S t e r n h e i m e r effect
The famous "Sternheimer effect" or "Sternheimer correction" (traditional

t e r m s ) i s a p a r t i c u l a r type of a f a r - c o n f i g u r a t i o n i n t e r a c t i o n e f f e c t . It is t h e
e f f e c t on the e l e c t r i c - q u a d r u p o l e h f s e l e c t r o n i c p a r a m e t e r of t h e m i x i n g
b e w e e n t h e c o n f i g u r a t i o n c o n s i d e r e d . . . . (n'i ') 4f 4 2 . . . . ( n i ) N and c o n f i g u r a t i o n s
of the type (n4L ' ) 4 i ' + 1 (ní )N (n"i ").
F r o m a p a r a m e t r i c point of v i e w , this s e c o n d - o r d e r e f f e c t i s t r i v i a l :
it m u l t i p l i e s t h e h f s c o n s t a n t b n i by (1+Ç) ( f « l ) , w h e r e Ç is i n d e p e n d e n t of
the l e v e l in t h e s t u d i e d c o n f i g u r a t i o n . A m a j o r w o r k of S t e r n h e i m e r s i n c e
1950 h a s b e e n to c o m p u t e ab initio v a l u e s of ? f o r m a n y c o n f i g u r a t i o n s in a
g r e a t n u m b e r of e l e m e n t s . E x e r c i s e : C o m p i l e l i s t of t h e r e l e v a n t Jl'-*SL "
e x c i t a t i o n s , f o r SL ' going f r o m 0 to 3.
232 BAUCHE
2.3.3. Relativity
We a l l b e l i e v e in r e l a t i v i t y , and we e v e n know that the D i r a c e q u a t i o n

a l l o w s u s to handle it in q u a n t u m m e c h a n i c s (at l e a s t f o r h y d r o g e n ; c o m p l i -
c a t i o n s a p p e a r a l r e a d y when we go to h e l i u m , w h e r e the B r e i t a p p r o x i m a t e
H a m i l t o n i a n m u s t be u s e d [1] ).
S a n d a r s and B e c k showed how to t a k e r e l a t i v i t y into account f o r h f s [10],
with the h e l p of e f f e c t i v e o p e r a t o r s . To be s h o r t , in , r e l a t i v i t y is a
s e c o n d r e a s o n f o r the a nJ! (i) and a n i ( s C ) to b e d i f f e r e n t and f o r t h e a n i ( s ) to b e
n o n - z e r o w h e n i = 0. F o r the e l e c t r i c p a r t , r e l a t i v i t y c o n t r i b u t e s to fcy , but
a l s o i n t r o d u c e s new e f f e c t i v e o p e r a t o r s with a n g u l a r p a r t s w ( n ) 2 and w
2.3.4. H y p e r f i n e - s t r u c t u r e anomaly
In our m o d e l , when the f i r s t - o r d e r p e r t u r b a t i o n m e t h o d is a s a t i s f a c t o r y

a p p r o x i m a t i o n to h f s c o m p u t a t i o n s (i. e. a l m o s t a l w a y s ) , the m a g n e t i c hfs
e n e r g y AW is the p r o d u c t of / I by a p u r e l y e l e c t r o n i c f a c t o r . So, when the
h f s c o n s t a n t s A of a given l e v e l can be m e a s u r e d f o r two d i f f e r e n t i s o t o p e s
1 and 2, they should a g r e e with the r e l a t i o n A-^j/Mj = ^ is Possible
to t r y to c h e c k t h i s r e l a t i o n , b e c a u s e ju c a n be m e a s u r e d d i r e c t l y (by NMR,
f o r e x a m p l e ) . Owing to the g r e a t a c c u r a c y of a l l t h e s e m e a s u r e m e n t s , the
r e l a t i o n is s o m e t i m e s found not to hold true. 1 The quantity
is c a l l e d the h y p e r f i n e - s t r u c t u r e a n o m a l y f o r a l e v e l if isotope 2 is h e a v i e r
than i s o t o p e 1. We m a y a s k why Д 1 2 can s o m e t i m e s d i f f e r f r o m 0.
F u n d a m e n t a l l y we find h e r e a p r o b l e m w h e r e t h e s e c o n d o r d e r of p e r t u r -
b a t i o n c o n t r i b u t e s , but m o r e p r e c i s e l y the s e c o n d o r d e r of the s u m of the
h y p e r f i n e s t r u c t u r e and i s o t o p e shift e f f e c t s ; to s p e a k m o r e s i m p l y , the
e l e c t r o n i c wave f u n c t i o n c h a n g e s a l i t t l e from one i s o t o p e to the other,
b e c a u s e the s p a t i a l e x t e n s i o n and d i s t r i b u t i o n of c h a r g e and m a g n e t i s m
c h a n g e . T h i s c h a n g e in the wave f u n c t i o n is a l m o s t l i m i t e d to the s - e l e c t r o n s ,
which " s p e n d s o m e t i m e " in the n u c l e u s . So the h y p e r f i n e - s t r u c t u r e a n o m a l y
c a n b e u s e d a s a t e s t f o r the p r e s e n c e of s p i n c o r e - p o l a r i z a t i o n .
E x e r c i s e s : (a) P r o v e that e v e r y s p e c t r a l line of e v e r y n a t u r a l c h e m i c a l

e l e m e n t is a g r o u p of s e v e r a l c o m p o n e n t s (only t h e v a r i o u s c a u s e s f o r line
b r o a d e n i n g often p r e v e n t the o b s e r v a t i o n of t h i s s t r u c t u r e ) ;
(b) Find out which two n a t u r a l c h e m i c a l e l e m e n t s p o s s e s no
h y p e r f i n e s t r u c t u r e in t h e i r s p e c t r a l l i n e s .
P A R T II: ISOTOPE SHIFT
3. ISOTOPE S H I F T : GENERAL
In the following we s h a l l c o n s i d e r two i s o t o p e s of the s a m e e l e m e n t , with

m a s s n u m b e r s A1 and A j and z e r o n u c l e a r s p i n s .
IAEA-SMR-12/7 233
Although t h e r e is h e r e no h f s , t h e r e r e m a i n two d i f f e r e n c e s b e t w e e n the

t r u e n u c l e u s and the v e r y s i m p l e d e s c r i p t i o n u s e d f o r s t u d y i n g e l e c t r o n i c
s t r u c t u r e [1 ] :
very simple description true nucleus

infinite n u c l e a r m a s s finite nuclear m a s s
point n u c l e u s finite nuclear volume
T h e f i r s t d i f f e r e n c e l e a d s to the m a s s i s o t o p e s h i f t , due to the f a c t that

the n u c l e u s is not the c e n t r e of g r a v i t y of the a t o m ; the s e c o n d d i f f e r e n c e
l e a d s to the f i e l d isotope s h i f t (or v o l u m e i s o t o p e s h i f t ) , owing to the f a c t
that the e l e c t r i c n u c l e a r p o t e n t i a l " s e e n " by the e l e c t r o n s is not Z e / r f r o m
r = 0 t o г = ю. Both t y p e s of i s o t o p e s h i f t a l w a y s c o - e x i s t .
3.1. C o - e x i s t e n c e of m a s s and field i s o t o p e s h i f t s
3.1.1. Mass shift
(a) The Hamiltonian
An obvious a r g u m e n t is the following: as the n u c l e u s m o v e s , i t s k i n e t i c

e n e r g y (p N ) 2 /2M m u s t b e added to the H a m i l t o n i a n . In a c o - o r d i n a t e s y s t e m ,
h o w e v e r , w h e r e the t o t a l m o m e n t u m is z e r o ( c e n t r e - o f - m a s s s y s t e m ) ,
p N = - Çp w h e r e pi is t h e m o m e n t u m of e l e c t r o n i. So we have i m m e d i a t e l y
t h e m a s s - s h i f t H a m i l t o n i a n in t e r m s of e l e c t r o n i c o p e r a t o r s : H =(1/2M)(£ Pj)'
T h i s H a m i l t o n i a n is the s u m of H ^ g = ( 1 / 2 M ) Ç ( p ^ C n o r m a l " o r " B o h r "
m a s s s h i f t ) and H SMS = ( l / M ) E (pj • pj ) ( " s p e c i f i c " m a s s s h i f t ) .
(b) N o r m a l m a s s s h i f t (NMS)
If we add H to the m a i n e l e c t r o n i c H a m i l t o n i a n [1]
we s e e t h a t the n o r m a l m a s s - s h i f t p a r t is e a s i l y c o m b i n e d with the e l e c t r o n i c

k i n e t i c e n e r g y and y i e l d s
w h e r e ц is t h e r e d u c e d m a s s , s u c h that 1/м = l / m + 1 / M . So, in the s a m e

way a s m e 4 / i l 2 is the only e n e r g y - d i m e n s i o n e d c o n s t a n t of the p r o b l e m when
i s o t o p e s h i f t i s a b s e n t , now ß e 4 / h 2 i s the only e n e r g y - d i m e n s i o n e d c o n s t a n t .
A p a r t f r o m t h i s d i f f e r e n c e , the two e q u a t i o n s (with and without H NMS ) a r e
e x a c t l y the s a m e . So E w i t h N M S = (ß/m) E w i t h o u t N M S .
Now, what is known e x p e r i m e n t a l l y (if we s u p p o s e N M S » S M S , which is
the c a s e ) is p r a c t i c a l l y E w i t h N M S . So we c a n d e t e r m i n e the c o n t r i b u t i o n of
NMS, which i s
234 BAUCHE
ДР = F F = p (1 S3L) = P
NMS with NMS without NMS with NMS \ p / M with NMS
AF ~ - Fe x
" ^ M S - M P
A c t u a l l y A E N M S ( e n e r g y d i f f e r e n c e b e t w e e n the c a s e s M =oo and M ôo) i s

of no i n t e r e s t ; we a r e r a t h e r i n t e r e s t e d in
M -M.
ДЕ (M = M ) - ДЕ
v x (M = M ) = — - m E
NMS 2 ^NMS Y M M exp.
1 2
o r even b e t t e r , in a t r a n s i t i o n a = or'J'-» aj, with
^ N M S (M 2 .E ' J ' ) - A E n m s (MJ,<*'J')j - [ДЕ ЫМЗ ( M 2 . a J ) - AE N M S ( M ^ J )
( isotope shift for level a'JM

and i s o t o p e s M j and M2 J
/isotope shift for level a J \
l and i s o t o p e s M j and IV^ J
with the f i n a l v a l u e
Ло =
19 W ^ 1 "
MjlVIg
1
^ w h e r e ста=
E(a'J') - E(aJ)
T h i s s h o w s t h a t the NMS in an a t o m i c l i n e d e p e n d s only on t h e w a v e

n u m b e r of t h e l i n e . T h e s i g n we have c h o s e n f o r it i s t h e u s u a l one: it i s
p o s i t i v e in a l l t r a n s i t i o n s , i . e . t h e c o m p o n e n t f o r t h e h e a v i e r i s o t o p e h a s t h e
l a r g e r w a v e n u m b e r . We c a n d r a w t h e e n e r g y s c h e m e a s shown in the
following:
a'j'
0, = 0(M| l<n) a2- o(ii2lm)
a J •
M =oo M = M. M = м 2 >м,
On t h i s s t u d y of the n o r m a l m a s s s h i f t we a l r e a d y s e e t h a t any i s o t o p e
s h i f t AO12 in a l i n e i s a " d i f f e r e n c e of d i f f e r e n c e s " : it c a n b e s e e n e i t h e r a s
t h e d i f f e r e n c e b e t w e e n Oj and <j2 o r a s t h e d i f f e r e n c e b e t w e e n the i s o t o p e
s h i f t s of two l e v e l s .
IAEA-SMR-12/7 235
3.1.2. Field shift
T h e p o t e n t i a l e n e r g y of one e l e c t r o n in the n u c l e a r e l e c t r i c f i e l d i s
V = - Z e 2 / r only f o r r > R , R b e i n g the r a d i u s of a s p h e r i c a l n u c l e u s . T h e
c u r v e s obtained f o r V a r e shown in the following.
Applying the f i r s t o r d e r of p e r t u r b a t i o n to t h e c a s e of one e l e c t r o n rü., we

obtain f o r the d i f f e r e n c e b e t w e e n the c a s e s R ^ O and R = 0
Ze2
ДЕ, V(r) + I V r ) | 2 r 2 dr
which is a p o s i t i v e quantity.
3.1.3. O r d e r s of m a g n i t u d e
(a) Mass shift
F o r m a s s s h i f t , the only l i n e quantity which is not e l e c t r o n i c is

(M 2 -M 1 )/M 1 M 2 ; it i s of the o r d e r of m a g n i t u d e of 1 / A M (A b e i n g the m a s s
n u m b e r ) . So t h e o r d e r of m a g n i t u d e of t h e m a s s s h i f t in an o p t i c a l line is
Hartree X ^ or H a r t r e e X ^ X - i—£2 m K
w h e r e A2 is a f a c t o r which can v a r y f r o m a few u n i t s (for h y d r o g e n ) to

60 000 ( f o r p l u t o n i u m ) .
T h e o r d e r of m a g n i t u d e of the m a s s s h i f t d e c r e a s e s r a p i d l y (°c 1 /А 2 ) a s
A i n c r e a s e s in t h e p e r i o d i c t a b l e .
(b) Field shift
F o r an a p p r o x i m a t e e v a l u a t i o n of field s h i f t we a s s u m e that the whole

n u c l e a r c h a r g e is l o c a t e d on the s p h e r e of r a d i u s R. T h e n V ( r ) = - Z e 2 / R f o r
0 < r < R . T h e field s h i f t is i m p o r t a n t only f o r s - e l e c t r o n s , whose wave
f u n c t i o n is n o n - z e r o f o r r = 0. We s u p p o s e that t h i s wave f u n c t i o n i s a l m o s t
c o n s t a n t in t h e n u c l e a r v o l u m e (a v e r y good a p p r o x i m a t i o n , a s R i s so s m a l l ) .
236 BAUCHE
We obtain
Z(;2r2
AF -
V°>l 2
H e r e e2 and |u n j ! (0)| 2 a r e t h e only e l e c t r o n i c q u a n t i t i e s . So we could conclude

that the o r d e r of m a g n i t u d e of AE fs i s s i m p l y H a r t r e e X R 2 / a 2 . H o w e v e r , as
in the c a s e of t h e m a s s s h i f t , we a r e i n t e r e s t e d in the g r o s s d e p e n d e n c e of
the f i e l d s h i f t on A. So we c o n s i d e r the quantity
R2
H a r t r e e X ^ X Z X a 3 | u „(0)| 2
f o r an o r d e r - o f - m a g n i t u d e e s t i m a t e ;
(a3| U n { (0)| 2 is d i m e n s i o n l e s s )
We now u s e the f o r m u l a R = r 0 A1^3, with r 0 ~ 1 f e r m i , a s w e l l as t h e f a c t that

| u n i ( 0 ) | d e p e n d s m a r k e d l y upon Z; u s i n g the f o r m u l a s f o r h y d r o g e n i c a t o m s [11],
we t a k e a d e p e n d e n c e in Z 3 .
The o r d e r of m a g n i t u d e of AE fs b e c o m e s
H a r t r e e X 4 - X Z4A2/3
a
and, b e t w e e n two i s o t o p e s w h o s e m a s s n u m b e r s d i f f e r by ДА = 2,
H a r t r e e X ^ - X Z 4 А" 1 / 3 , i . e . | X 10" 2 А п / 3 mK ( b e c a u s e Z ^ A / 2 )
T h e f i e l d s h i f t i n c r e a s e s r a p i d l y (« A 11 / 3 ) along the p e r i o d i c t a b l e .
Note: the f a c t o r A11^3 is r e l a t i v e l y c o r r e c t , but the c o n s t a n t f a c t o r is m u c h

too l a r g e a s we s h a l l show l a t e r (3.2. c. ).
3.1.4. T h e King g r a p h s
(a) Historical background. R e l a t i v e i s o t o p e s h i f t (RIS)
F o r m a n y y e a r s only t h e g e n e r a l t r e n d s of t h e two p a r t s of isotope s h i f t

w e r e t a k e n into a c c o u n t , t o g e t h e r with t h e i d e a that f o r Z < 3 0 (Zn)
( r e s p . > 54 (Xe)) only the m a s s ( r e s p . field) s h i f t w a s p r e s e n t , and that b e t w e e n
Z = 30 and Z = 54 the i s o t o p e s h i f t is v e r y s m a l l . C o n s e q u e n t l y , a s no a p p r e -
c i a b l e m i x i n g b e t w e e n the two e f f e c t s a p p e a r e d , the r e l a t i v e i s o t o p e s h i f t
(RIS) w a s the s a m e in a l l l i n e s of a given e l e m e n t :
RIS f o r A ^ A 2 , А 3 = Д а у Д а а 2
IAEA-SMR-12/44,46,48 237
Indeed we s e e t h a t , f o r e v e r y line,
RIS
= Щ Ч ^ Щ (only m a s s ehlft)
RIS = (only f i e l d s h i f t )
c 2 -q
where
Ze2 2,
C. = v( (r) + r dr
At high m a s s n u m b e r s the RIS f o r m a s s s h i f t is v e r y c l o s e to u n i t y , f o r

A j , A 2 and A 3 in a r i t h m e t i c p r o g r e s s i o n . T h e RIS f o r f i e l d s h i f t d e p e n d s on
t h e f o r m of t h e n u c l e u s .
With the i m p r o v e m e n t in e x p e r i m e n t a l a c c u r a c y ( e s p e c i a l l y t h r o u g h the
u s e of e n r i c h e d i s o t o p e s ) , S t r i g a n o v and c o - w o r k e r s [12] could m e a s u r e in
1962 a lot of l i n e s of Sm I f o r a s e r i e s of i s o t o p e s , p r o v i n g that the RIS
c h a n g e s m a r k e d l y f r o m s o m e l i n e s to o t h e r s .
Soon t h e r e a f t e r King [13] i n t e r p r e t e d t h i s v a r i a t i o n by the m i x i n g of
m a s s and f i e l d s h i f t s . Indeed, if both a r e of c o m p a r a b l e m a g n i t u d e , we
can w r i t e
М
з-М2 , .
A
°*23 1 Д Л + (С3 C 2 ) E a
RIS. =
M 2 - M]L±K (C2-Cl)Ea
MjM2 a+
f o r the RIS in line a, K a and E a b e i n g p u r e l y e l e c t r o n i c m a s s (SMS included)

and field f a c t o r s , d e p e n d i n g only on the line a. E v i d e n t l y RIS d e p e n d s on a.
(b) The King g r a p h
King p r o p o s e d to r e p r e s e n t g r a p h i c a l l y t h i s s i t u a t i o n . If one d e f i n e s
and
A A
? = До15 • »• •>• • (line b)
l] A. - A .
] i
then
E / E
s 5 К
=ЁГ Ч .- Ér15*
b b
f o r e v e r y p a i r (i, j) of i s o t o p e s . So, in c o - o r d i n a t e s , e a c h p a i r of l i n e s
( a , b ) m u s t c o r r e s p o n d to a s t r a i g h t l i n e (see f i g u r e ) , independent of the
i s o t o p e s c o n s i d e r e d ( s e e a l s o [14] f o r s u c h a g r a p h ) .
238 BAUCHE
E a_
Slope
E»
I n t e r c e p t ОМ
g (line b)
T h e i n t e r c e p t and the s l o p e of t h e line a r e p u r e l y e l e c t r o n i c q u a n t i t i e s .

Since 1963 e x p e r i m e n t a l i s t s have d e t e r m i n e d m a n y King l i n e s with good
a c c u r a c y (the m e a s u r e m e n t s m u s t be v e r y a c c u r a t e f o r t h e t e s t on w h e t h e r
the p o i n t s a r e aligned to be s i g n i f i c a n t ) .
One i m p o r t a n t r e s u l t is the following. F o r odd i s o t o p e s , whose l i n e s
a r e a f f e c t e d by t h e h y p e r f i n e - s t r u c t u r e p h e n o m e n o n , it is e a s i l y shown that
the c e n t r e of g r a v i t y of the s t r u c t u r e is at the p l a c e w h e r e the line would b e
in the a b s e n c e of h f s . ( E x e r c i s e : p r o v e t h a t , f o r h f s of a r b i t r a r y m u l t i p o l a r
t y p e , the c e n t r e of g r a v i t y of any l e v e l s t r u c t u r e is at t h e e n e r g y t h e l e v e l
would have in t h e a b s e n c e of h f s , if the f i r s t o r d e r of p e r t u r b a t i o n t h e o r y is
s u f f i c i e n t ( g e n e r a l c a s e ) . ) H o w e v e r , we c a n plot in t h e King g r a p h t h e p o i n t s
f o r even and odd i s o t o p e s s e p a r a t e l y . It will b e a l m o s t c e r t a i n t h a t , in
s o m e c a s e s , s u c h p o i n t s " f o r odd i s o t o p e s " d e f i n i t e l y do not lie on the line
obtained f o r t h e e v e n i s o t o p e s .
A n o t h e r way of c o n s i d e r i n g the King line i s the following. Denote by
y = K a and x = K b t h e unknown q u a n t i t i e s K a and Kfe. T h e s e q u a n t i t i e s a r e
r e l a t e d by the l i n e a r e q u a t i o n y = a x + ß , w h e r e a= E a / E b a n d ß = K a - ( E a / E b ) K b
a r e given e x p e r i m e n t a l q u a n t i t i e s . T h i s e q u a t i o n is e x a c t l y the equation of
the King line. Suppose now that s e v e r a l King l i n e s a r e d r a w n with a c o m m o n
line " a " . It would then b e enough to know (by an a - p r i o r i t h e o r e t i c a l c o m -
p u t a t i o n ? ) t h e v a l u e of K j to d e d u c e i m m e d i a t e l y t h e K^, - v a l u e s .
x : l i n e s "b'tt
у : line "a"
IAEA-StoR-12/7 239
3.2. Theoretical approaches
(a) P a r a m e t r i c study of s p e c i f i c m a s s shift plus field s h i f t
S u b t r a c t i n g the NMS f r o m t h e e x p e r i m e n t a l r e l a t i v e v a l u e s of t h e s h i f t s
(between i s o t o p e s 1 and 2) of l e v e l s of a given c o n f i g u r a t i o n , we c a n t r y and
" i n t e r p r e t " the r e s i d u a l s h i f t s by m e a n s of the p a r a m e t r i c m e t h o d [15].
(b) Mass shift
( a ) V a r i o u s a u t h o r s have t r i e d t o e v a l u a t e t h e s p e c i f i c m a s s s h i f t by
" a b - i n i t i o " m e t h o d s , but the r e s u l t s achieved s o f a r [16] w e r e r e l a t i v e l y poor.
(j3) F o r m a l e x p r e s s i o n s f o r r e l a t i v i t y c o r r e c t i o n s to the m a s s s h i f t w e r e
given by Stone [17]; the c o r r e s p o n d i n g o p e r a t o r s act in the n o n - r e l a t i v i s t i c
s p a c e . No c o m p l e t e l y r e l a t i v i s t i c e x p r e s s i o n f o r t h e m a s s s h i f t is yet known.
T h e i n t e r p r e t a t i o n of s h i f t s in Ne I p r o v e s t h e e x i s t e n c e of e f f e c t s of
r e l a t i v i t y [18].
(c) Field shift
( а ) T h e f i r s t a t t e m p t to e v a l u a t e field s h i f t t h e o r e t i c a l l y w a s m a d e by
B a r t l e t t [ 1 9 ] , who u s e d n o n - r e l a t i v i s t i c e l e c t r o n i c f u n c t i o n s . H o w e v e r , the
e l e c t r o n h a s a m a r k e d r e l a t i v i s t i c c h a r a c t e r when it is v e r y c l o s e to o r
i n s i d e t h e n u c l e u s ( e x e r c i s e : c o m p u t e the n o n - r e l a t i v i s t i c k i n e t i c e n e r g y of a
I s - e l e c t r o n , in t h e h y d r o g e n a t o m i c s p e c t r u m , when it is located at r = 1 f e r m i ,
which is a l m o s t t h e r a d i u s of the p r o t o n ) . F o r a c o r r e c t e v a l u a t i o n we m u s t
c o n s i d e r t h e D i r a c equation f o r one e l e c t r o n at v e r y s m a l l v a l u e s of r [20].
(ß) In the c a s e of s e v e r a l e l e c t r o n s the s c r e e n i n g f a c t o r s a r e i n t r o d u c e d
p h e n o m e n o l o g i c a l l y . T h e y c a n b e computed a p p r o x i m a t e l y by a b - i n i t i o
m e t h o d s [21].
(7) T h e study of i s o t o p e s h i f t in a t o m i c t r a n s i t i o n s of m u o n i c a t o m s
( a t o m s w h e r e one of t h e e l e c t r o n s is r e p l a c e d by a m u o n ) and in the X - r a y
t r a n s i t i o n s of o r d i n a r y a t o m s y i e l d s e a s i l y the f i e l d s h i f t s , b e c a u s e t h e r e the
SMS is n e g l i g i b l e .
(б) As c o n c e r n s t h e n u c l e u s , the isotope s h i f t g i v e s an i n f o r m a t i o n on a
quantity c l o s e to the r o o t - m e a n - s q u a r e value of i t s c h a r g e d i s t r i b u t i o n . Is
t h i s quantity of any i n t e r e s t to the n u c l e a r p h y s i c i s t ?
REFERENCES
[1] FENEUILLE, S . , t h e s e P r o c e e d i n g s .
[2] S C H W A R T Z , C . , P h y s . R e v . 9 7 (1955) 3 8 0 a n d 105 (1957) 1 7 3 .
MALLI, G . , FRAGA, S . , C a n . J . P h y s . 4 5 ( 1 9 6 7 ) 219.
[3] RAMSEY, N . F . , N u c l e a r M o m e n t s , John W i l e y a n d Sons, N e w York ( 1 9 5 3 ) .
[4] KOPFERMANN, H . , N u c l e a r M o m e n t s ( t r a n s l a t i o n ) . A c a d e m i c Press, N e w York ( 1 9 5 8 ) .
[5] KUHN, H . G . , A t o m i c s p e c t r a , L o n g m a n s , London ( 1 9 6 9 ) .
[6] EDMONDS, A . R . , A n g u l a r M o m e n t u m i n Q u a n t u m M e c h a n i c s , P r i n c e t o n U n i v e r s i t y Press ( 1 9 6 0 ) .
[7] AGRAGAM, A . , H O R O W I T Z , J . , PRYCE, M . H . L . , P r o c . R . S o c . , A230 ( 1 9 5 5 ) 1 6 9 .
[8] HARVEY, J . S . M . , P r o c . R . S o c . 2 8 5 (1965) 5 8 1 .
[9] JUDD, B . R . , H y p e r f i n e S t r u c t u r e s in t h e A t o m i c 2 p - S h e l l , in "La S t r u c t u r e H y p e r f i n e M a g n é t i q u e des
A t o m e s e t des M o l é c u l e s " , Editions du C . N . R . S . , Paris ( 1 9 6 7 ) .
[10] SANDARS, P . G . H . , BECK, J . . P r o c . R . S o c . A 2 8 9 ( 1 9 6 5 ) 1 0 8 .
2 4 0 BAUCHE
[11] CONDON, E . U . , SHORTLEY, G . H . , T h e T h e o r y of A t o m i c S p e c t r a , C a m b r i d g e U n i v e r s i t y Press ( 1 9 5 1 ) .

[12] STRIGANOV, A . R . , KATULIN, V . A . , ELISEEV, V . V . , O p t . S p e c t r o s c . 12 (1962) 9 1 .
[13] KING, W . H . , J . O p t . S o c . A m . 5 3 (1963) 6 3 8 .
[14] KING, W . H . , J . P h y s . В ( A t o m . M o l e c . P h y s . ) 4 (1971) 2 8 8 .
[15] STONE, A . P . , P r o c . P h y s . S o c . 74 (1959) 4 2 4 Г
BAUCHE, J . , P h y s i c a 4 4 ( 1 9 6 9 ) 2 9 1 .
[16] BAUCHE, J . , CRUBELLIER, A . , J . P h y s . (1969) c o l l o q u e C l .
[17] S T O N E , A . P . , P r o c . P h y s . S o c . 77 (1961) 786 a n d 81 (1963) 8 6 8 .
[18] BAUCHE, J . . KELLER, J . C . , P h y s . L e t t . 36A (1971) 2 1 1 .
[19] BARTLETT, J . H . , N a t u r e 128 (1932) 4 0 8 .
[20] RA С А Н , G - , N a t u r e 1 2 9 (1932) 7 2 3 .
ROSENTHAL, J . E . . BREIT, G . , P h y s . R e v . 4 1 (1932) 4 5 9 .
HUMBACH, W . , Z . P h y s . 1 4 1 (1955) 5 9 .
[21] WILSON, M . , P h y s . R e v . Г76 (1968) 5 8 .
IAEA-S M R - 1 2 / 4 5
HIGHLY EXCITED ATOMS
I . C . PERCIVAL
University of Stirling,
Stirling,
Scotland, United Kingdom
Abstract
HIGHLY EXCITED A T O M S .
1. I n t r o d u c t i o n ; 2 . E l e m e n t a r y p r o p e r t i e s ; 3. T h e c o r r e s p o n d e n c e p r i n c i p l e for i n t e n s i t y of r a d i a t i o n ;
4. Classical collisions; 5. C l a s s i c a l c r o s s - s e c t i o n s ; 6. D i s c r e t e s t a t e s a n d c o r r e s p o n d e n c e p r i n c i p l e s ;
7 . Discussion of l i t e r a t u r e . Appendix.
1. INTRODUCTION
By highly excited we m e a n an a t o m o r ion which h a s an e l e c t r o n whose

b i n d i n g e n e r g y i s v e r y s m a l l c o m p a r e d with i t s b i n d i n g e n e r g y in t h e g r o u n d
s t a t e . P r o p e r t i e s of s u c h a t o m s d i f f e r c o n s i d e r a b l y f r o m t h o s e of o t h e r
atoms or ions.
H i g h l y e x c i t e d a t o m s a r e found in p l a s m a s , w h e r e t h e y p l a y a n i m p o r t a n t
r o l e in r e c o m b i n a t i o n . T h e s e p l a s m a s m a y b e f o u n d in t h e l a b o r a t o r y , in
s t e l l a r a t m o s p h e r e s o r i n i n t e r s t e l l a r s p a c e . T h e y m a y not a l w a y s b e
o b s e r v e d in a l l t h e s e r e g i o n s but t h e y a r e d i r e c t l y o b s e r v e d in h i g h l y i o n i z e d
r e g i o n s (HII r e g i o n s ) of s p a c e , in t h e n e i g h b o u r h o o d of hot s t a r s a n d a l s o i n
t h e HI r e g i o n s w h i c h a r e c o o l e r a n d h a v e a r e l a t i v e l y low d e g r e e of
i o n i z a t i o n . In e a c h c a s e , r a d i o f r e q u e n c y t r a n s i t i o n s a r e o b s e r v e d b e t w e e n
close-lying states using r a d i o - t e l e s c o p e s .
F o r e x a m p l e , t h e t r a n s i t i o n H(109a), w h i c h i s
H(n = 110) - H(n = 109) + hv
w h e r e v i s in t h e r a d i o f r e q u e n c y r a n g e .
S t a t e s of a r a t h e r l o w e r l e v e l of e x c i t a t i o n m a y b e of p r a c t i c a l i m p o r t a n c e
i n t h e p r o d u c t i o n of hot l a b o r a t o r y p l a s m a s . T h e s e p l a s m a s a r e r e q u i r e d if
we w a n t to p r o d u c e c o n t r o l l e d t h e r m o n u c l e a r r e a c t i o n s , n e e d e d t o e a s e t h e
W o r l d ' s energy p r o b l e m s in the coming d e c a d e s .
T h e r e i s m o r e t h a n one p o s s i b l e m e a n s to t h i s end: t h a t w h i c h i n v o l v e s
h i g h l y e x c i t e d a t o m s i s t h e p r o d u c t i o n of p l a s m a s in a m a g n e t i c f i e l d by
i n j e c t i o n of a f a s t (10 keV o r m o r e ) b e a m of d e u t e r i u m a t o m s . In the e a r l y
s t a g e s of p l a s m a p r o d u c t i o n , g r o u n d - s t a t e a t o m s a r e not s i g n i f i c a n t l y
i o n i z e d b y t h e p l a s m a , and a t o m s in a low s t a t e of e x c i t a t i o n (n <, 7) d e c a y
r a p i d l y to the I s o r 2s s t a t e s . However, highly excited s t a t e s have a v e r y
weakly bound o r b i t a l e l e c t r o n which is r e l a t i v e l y easily s t r i p p e d f r o m the
d e u t e r i u m n u c l e u s to c o n t r i b u t e a n e w ion to t h e p l a s m a . T y p i c a l l y , a t o m s
w i t h p r i n c i p a l q u a n t u m n u m b e r n l e s s t h a n 16 a r e i n v o l v e d .
So w e s e e t h a t t h e a r e a s of i n t e r e s t in h i g h l y e x c i t e d a t o m s a r e l a r g e .
H i g h l y e x c i t e d s t a t e s a r e c o m m o n l y o b s e r v e d in t h e u . v . a n d in
t h e v i s i b l e . T h e h i g h e s t i s t h e o b s e r v a t i o n of a s t a t e of B a with n = 105 by
2 4 1
2 4 2 PERCIVAL
m e a n s of a 3 0 - f t (9 m) u . v . s p e c t r o g r a p h at t h e A r g o n n e N a t i o n a l L a b o r a t o r y
in U . S . A . [ G a r t o n a n d T o m k i n s (unpublished)] . T h i s work c o n c e r n s
t r a n s i t i o n s f r o m a highly e x c i t e d state t o a low s t a t e .
T h e o b s e r v a t i o n s we c a n m a k e in t h e l a b o r a t o r y a r e c o m p l e m e n t a r y to
t h o s e m a d e by a s t r o n o m e r s . T h e f o r m e r involve t r a n s i t i o n s f r o m a highly
e x c i t e d s t a t e to a l o w - l y i n g s t a t e ; t h e l a t t e r t r a n s i t i o n s b e t w e e n highly
e x c i t e d s t a t e s w h e r e o b s e r v a t i o n s a r e m a d e of the " r a d i o - r e c o m b i n a t i o n
l i n e s " . T h e d i s t i n c t i o n b e t w e e n the above o b s e r v a t i o n s i s an i m p o r t a n t one.
A highly e x c i t e d s t a t e i s c h a r a c t e r i z e d by q u a n t u m n u m b e r s (Í, m) in
a d d i t i o n to t h e p r i n c i p a l q u a n t u m n u m b e r n, and t h e i m p o r t a n t (Í, m) s t a t e s
in t h e two c a s e s d i f f e r :
for radio-recombination i , m < , n
in t h e l a b o r a t o r y I , m ~ 0 , 1 , 2, 3.
B e c a u s e t h e p r o p e r t i e s of highly e x c i t e d s t a t e s d i f f e r so m u c h f r o m
t h o s e of l o w - s t a t e a t o m s , t h e a p p r o p r i a t e t h e o r y a l s o d i f f e r s . In p a r t i c u l a r ,
f o r highly e x c i t e d a t o m s the c l a s s i c a l m o d e l of t h e a t o m can b e t a k e n
s e r i o u s l y . M e t h o d s can b e used which a r e at b e s t doubtful f o r low s t a t e s
of e x c i t a t i o n .
2. ELEMENTARY PROPERTIES
C o n s i d e r t h e B o h r m o d e l of a c l a s s i c a l e l e c t r o n moving in a c i r c u l a r
o r b i t a r o u n d a p r o t o n to r e p r e s e n t t h e g r o u n d s t a t e (n = 1 ) of t h e h y d r o g e n
a t o m , w h e r e t h e m o d e l i s evidently v e r y c r u d e .
T A B L E I. E L E M E N T A R Y P R O P E R T I E S O F HIGHLY E X C I T E D S T A T E S
I II III IV
Property n = 1 Arbitrary n n = 110
Binding e n e r g y U n 1 Ry = 1 3 . 6 eV Ry/n 2 1 . 1 X 10"3 eV
Radius a R of a 0 = aL n2a0 6 . 4 X 10"5 c m

Bohr o r b i t = 5 . 3 X 1СГ9 c m
G e o m e t r i c cross - 8. 8 X 1 0 " " cm2 n4iraj 1 . 3 X 10"" c m

s e c t i o n ira^j
rms velocity c a = v j = 2 . 2 X 10 s vj/n 2 . 0 X 10 6 c m / s

of e l e c t r o n v n cm/s
3„
Period T n 1 . 5 X 10"1S s n T! 2. 0 X 10" 1 0 s
Fundamental Vi - n"3!^ 4 . 9 4 1 X 10 9 Hz
classical frequency vc 6 . 5 7 6 X 10 1 5 Hz [(n - [ 5 . 0 0 9 X 10® H z ]
Classical wave >4 1 = 2 R H 2n"3RH 0.1648 cm"1

n u m b e r X."1 = 2 . 1 9 4 X 10 5 c m " 1 [2(n - £)"3 R H ] [0.1671 cm"1 ]
Ouantal na None n - i 5 . 009 M H z

frequency [n(n - l)]2
IAEA-SMR-12/44,46,48 243
T h e g e o m e t r i c c r o s s - s e c t i o n g i v e s a good i d e a of the e f f e c t i v e s i z e of
t h e a t o m , t h e r m s v e l o c i t y is e x a c t l y r i g h t , but the c l a s s i c a l f r e q u e n c y h a s
no m e a n i n g . T h e c l a s s i c a l p r o p e r t i e s of a highly e x c i t e d s t a t e can b e
o b t a i n e d f r o m t h o s e of t h e g r o u n d s t a t e by c e r t a i n s c a l i n g l a w s , a s s e e n in
c o l u m n s III and IV of T a b l e I.
S t a r t i n g with t h e q u a n t a l e x p r e s s i o n f o r t h e e n e r g y we find t h e H(110)
a t o m s a r e so v e r y weakly bound ( 1 . 1 X 10" 3 eV) that p a r t i c l e s at r o o m
t e m p e r a t u r e (1/40 eV) h a v e enough e n e r g y to d e s t r o y t h e m . Only low d e n s i t y
can s a v e t h e m .
A c c o r d i n g to C o u l o m b ' s l a w t h e o r b i t a l r a d i u s of a c h a r g e d p a r t i c l e
bound to a n o t h e r one t y p i c a l l y v a r i e s i n v e r s e l y with t h e e n e r g y , so t h e m e a n
B o h r r a d i u s f o r an H a t o m v a r i e s a s n 2 . T h e s i z e of an H(110) a t o m i s
t y p i c a l of a s m a l l b i o l o g i c a l o r g a n i s m . If it w e r e s o l i d it could b e s e e n
e a s i l y with an o p t i c a l m i c r o s c o p e . It is a s big when c o m p a r e d to a t y p i c a l
g r o u n d - s t a t e a t o m as a g r o u n d - s t a t e a t o m i s c o m p a r e d to i t s n u c l e u s . By
analogy, t h e s t r u c t u r e of t h e i o n i c c o r e of a highly e x c i t e d a t o m c a n usually
b e n e g l e c t e d . T h e c o r e is d i s t i n g u i s h e d only by i t s c h a r g e and m a s s , except
f o r r e l a t i v e l y v e r y s m a l l e f f e c t s a n a l o g o u s to t h e h y p e r f i n e s t r u c t u r e of
o r d i n a r y a t o m s . To t h i s e x t e n t , all highly e x c i t e d a t o m s a r e t h e s a m e , t h e i r
p r o p e r t i e s depending p r i m a r i l y on t h e c h a r g e of the c o r e and t h e q u a n t u m
n u m b e r s of the highly e x c i t e d e l e c t r o n s . E v e n a m o l e c u l a r ion c o r e m a k e s
little d i f f e r e n c e .
F r o m K e p l e r ' s l a w s of p l a n e t a r y m o t i o n , t h e p e r i o d of the e l e c t r o n in
i t s o r b i t s c a l e s a s the 3 / 2 p o w e r of the m e a n r a d i u s . F r o m t h i s we obtain
the f u n d a m e n t a l c l a s s i c a l f r e q u e n c y f o r a highly e x c i t e d a t o m , v i z .
v c = n" 3 vc (2.1)
n l \ • )
w h e r e v^ i s the " f r e q u e n c y " of the c l a s s i c a l a t o m i c m o d e l f o r t h e g r o u n d

s t a t e . F o r c i r c u l a r o r b i t s with m a x i m u m a n g u l a r . m o m e n t u m f o r fixed
e n e r g y U n , only t h e f u n d a m e n t a l f r e q u e n c y i s e m i t t e d (this c o r r e s p o n d s to
t h e q u a n t u m m e c h a n i c a l r u l e t h a t if I = jf m a x , a t r a n s i t i o n with A t = + 1 i s
i m p o s s i b l e ) . F o r e l l i p t i c o r b i t s with s m a l l e r a n g u l a r m o m e n t u m , t h e r e a r e
F o u r i e r c o m p o n e n t s of the m o t i o n at t h e h a r m o n i c f r e q u e n c i e s 2vc, 3v°, e t c . ,
which c o r r e s p o n d to q u a n t a l t r a n s i t i o n s with change Д п in t h e p r i n c i p a l
q u a n t u m n u m b e r of Д п = 2 , 3 , . . . e t c . F o r t h e q u a n t a l a t o m , t h e s e t r a n s i t i o n s
h a v e f r e q u e n c i e s which a r e not e x a c t m u l t i p l e s of t h e f u n d a m e n t a l f r e q u e n c y ,
but it i s hot too bad an a p p r o x i m a t i o n when Д п « п.
F r o m c l a s s i c a l f r e q u e n c i e s , following B o h r , we can obtain an e s t i m a t e
of t h e e n e r g y d i f f e r e n c e b e t w e e n i n i t i a l and f i n a l s t a t e s of an o p t i c a l t r a n s i t i o n
by u s i n g t h e P l a n c k r e l a t i o n
Д Е = \w = (2.2)
T h i s i s a d i r e c t a p p l i c a t i o n of B o h r ' s c o r r e s p o n d e n c e p r i n c i p l e f o r
frequencies.
T h e c o r r e s p o n d e n c e p r i n c i p l e i s v a l i d in t h e l i m i t of high q u a n t u m
n u m b e r s , and f r o m T a b l e I we s e e that it i s c l e a r l y m u c h b e t t e r f o r n = 110
t h a n f o r n = 1, a s we would e x p e c t .
In q u a n t u m o r wave m e c h a n i c s , the wave f u n c t i o n s of highly e x c i t e d
s t a t e s have v e r y m a n y o s c i l l a t i o n s (nodes), about 10 6 f o r n = 110. T r a d i t i o n a l
q u a n t a l m e t h o d s , s u c h a s c l o s e - c o u p l i n g , f o r t r e a t i n g the c o l l i s i o n s with
244 PERCIVAL
s u c h a t o m s r e q u i r e the n u m e r i c a l r e p r e s e n t a t i o n of t h e wave f u n c t i o n s in a
c o m p u t e r , and the n u m b e r of r e a l n u m b e r s r e q u i r e d to r e p r e s e n t s u c h a
wave f u n c t i o n i s at l e a s t a s l a r g e as the n u m b e r of o s c i l l a t i o n s . F u r t h e r m o r e
one n e e d s to c o n s i d e r a p p r o x i m a t e l y 10 6 d i f f e r e n t wave f u n c t i o n s (n in e a c h
of the t h r e e d i m e n s i o n s ) in o r d e r to s o l v e t h e c o l l i s i o n p r o b l e m . Obviously
when we a r e d e a l i n g with a n o n - s e p a r a b l e s y s t e m t h i s is a v e r y g r e a t
h a n d i c a p . T h e r e a r e m e t h o d s of s i m p l i f y i n g the q u a n t a l p r o b l e m by taking
a d v a n t a g e of the l a r g e n u m b e r of o s c i l l a t i o n s . T h e s e m e t h o d s a r e e i t h e r
r e l a t i v e l y r o u g h , o r they r e s u l t in e x p r e s s i o n s which can o f t e n be obtained
m o r e s i m p l y by c l a s s i c a l m e t h o d s o r m e t h o d s b a s e d on the c o r r e s p o n d e n c e
principle.
T h e c o r r e s p o n d e n c e p r i n c i p l e s that we s h a l l u s e can a l l be d e r i v e d f r o m
the S c h r ö d i n g e r o r H e i s e n b e r g f o r m s of q u a n t u m m e c h a n i c s . When t h i s i s
done they can b e applied d i r e c t l y to a wide v a r i e t y of p h y s i c a l p r o b l e m s .
C l a s s i c a l and c o r r e s p o n d e n c e p r i n c i p l e m e t h o d s should not be r e g a r d e d a s
an a l t e r n a t i v e m e t h o d to q u a n t u m m e c h a n i c s , but a s a m e t h o d of applying
q u a n t u m m e c h a n i c s which i s a p p r o p r i a t e to highly e x c i t e d s t a t e s .
3. C O R R E S P O N D E N C E P R I N C I P L E F O R INTENSITY O F RADIATION
B o h r w a s able to p r e d i c t the a p p r o x i m a t e i n t e n s i t y of s p o n t a n e o u s l y
e m i t t e d r a d i a t i o n b e t w e e n highly e x c i t e d s t a t e s by s u p p o s i n g that the m e a n
p o w e r W e m i t t e d in t h e t r a n s i t i o n n n1 t e n d s to c o i n c i d e with t h e m e a n
p o w e r W c e m i t t e d at the c o r r e s p o n d i n g c l a s s i c a l f r e q u e n c y :
If ДЕ i s the e n e r g y d i f f e r e n c e , and A is the quantal t r a n s i t i o n p r o b a b i l i t y ,
then
AAE^WC (3.1)
C o n s i d e r a c l a s s i c a l h y d r o g e n a t o m , and f o r s i m p l i c i t y s u p p o s e that
the n u c l e u s h a s infinite m a s s and is at r e s t at t h e o r i g i n of o u r c o - o r d i n a t e
s y s t e m . Let (g ,rj) b e t h e c o - o r d i n a t e s of t h e e l e c t r o n in the p l a n e of i t s
e l l i p t i c m o t i o n . Suppose that t h e unit v e c t o r f points in t h e d i r e c t i o n of the
p e r i h e l i o n (the c l o s e s t point of t h e e l e c t r o n to t h e n u c l e u s ) , a s in F i g . l .
T h e e l e c t r o n m o v e s in a p o s i t i v e , a n t i - c l o c k w i s e s e n s e in t h e (Ç,r?)
p l a n e . F r o m t h e s t a n d a r d t h e o r y of p l a n e t a r y m o t i o n , a s given by Landau
and L i f s h i t s (1969), in t e r m s of a p a r a m e t e r u which i s c a l l e d t h e ' e c c e n t r i c
a n o m a l y ' , we h a v e
f = a ( c o s u - e) r) = a(l - e 2 ) ^ s i n u (3.2)
w h e r e e i s t h e e c c e n t r i c i t y of t h e orbit a n d 2a i s t h e l e n g t h of t h e m a j o r
a x i s of t h e e l l i p s e .
T h e t i m e т i s given e x p l i c i t l y in t e r m s of u by
шт = u - e s i n u (3. 3)
T h e s e e q u a t i o n s m a y be v e r i f i e d by s u b s t i t u t i o n into N e w t o n ' s l a w s of m o t i o n .
S e m i - m a j o r a x i s a a n d f u n d a m e n t a l a n g u l a r f r e q u e n c y u a r e given in t e r m s
of the i o n i z a t i o n e n e r g y U by
IAEA-SMR-12/44,46,48 245
e2 2
- П ^
w h e r e e i s t h e c h a r g e of the e l e c t r o n and m e i s i t s m a s s . Note t h a t both a

and w a r e i n d e p e n d e n t of t h e e c c e n t r i c i t y e f o r a given U.
N T h e e c c e n t r i c i t y e i s r e l a t e d to the c l a s s i c a l a n g u l a r m o m e n t u m I e
through the equation
1 = (3.5)
m e4
e
C i r c u l a r o r b i t s with e = 0 a r e t h e c l a s s i c a l o r b i t s of m a x i m u m a n g u l a r
momentum
i
f o r a g i v e n U. T h e y c o r r e s p o n d t o q u a n t a l s t a t e s of m a x i m u m a n g u l a r
m o m e n t u m q u a n t u m n u m b e r i m a x = n - 1. T h e s t r a i g h t - l i n e o r b i t s of l e n g t h
2a, with e = 1 c o r r e s p o n d t o q u a n t a l s - s t a t e s .
FIG. 1. C o - o r d i n a t e s y s t e m for e l e c t r o n o r b i t a l m o t i o n .
In o r d e r t o apply t h e c o r r e s p o n d e n c e p r i n c i p l e we h a v e t o o b t a i n t h e
F o u r i e r c o m p o n e n t s of t h e m o t i o n with r e s p e c t to t h e t i m e r , a s w a s done
f o r p l a n e t a r y m o t i o n by L a g r a n g e in 1790:
f ( T ) = Y €s e x p ( - i s i o r ) (3.7)
S = - CO
w h i c h g i v e s us by t h e F o u r i e r t h e o r e m
T = 271 /ш
€S f С (т)exp(ISCOT)dr (3.8)
0
2тг
= J ? (u) (1 - e c o s u) exp {is(u - e sinu)}du (3.9)
о
246 PERCIVAL
therefore
sg s = a JJ (se), (s Ф 0) (3.10)
u s i n g t h e s t a n d a r d i n t e g r a l f o r m f o r t h e B e s s e l f u n c t i o n J s (x).
Of g r e a t e r i n t e r e s t f o r r a d i a t i o n a n d c o l l i s i o n t h e o r y i s t h e v e l o c i t y ,
whose and r j - c o m p o n e n t s a r e
v ,ts = - i u a j 's 4( s e )'

(3.11)
v, = ш a (e - 1)* J (se)
N o t e t h a t f o r c i r c u l a r o r b i t s (e = 0) t h e only n o n - z e r o c o e f f i c i e n t s a r e f o r
s = ± 1 , a n d it i s t h i s w h i c h r e s t r i c t s e m i s s i o n t o t h e f u n d a m e n t a l f r e q u e n c y .
F r o m L a n d a u a n d L i f s h i t s ( C l a s s i c a l T h e o r y of F i e l d s (1971) § 67) the
i n t e n s i t y o r p o w e r r a d i a t e d into the (s - 1 )th h a r m o n i c of f r e q u e n c y su i s
4 s 4 u 2 e 2 i-> i 2
: =
s " T T - К I (3.12)
v V +
s = SS 5 \ s "
therefore
= 4 s W a 2 ( J , 2 ( s e ) + (e-2 . 1)J (se)) (3.13)
s
3c
B y a v e r a g i n g o v e r the d i s t r i b u t i o n in e c c e n t r i c i t y , w h i c h in m o s t
c i r c u m s t a n c e s i s u n i f o r m i n e 2 , b e t w e e n 0 a n d 1, w e o b t a i n a c o r r e s p o n d e n c e
p r i n c i p l e f o r t h e o s c i l l a t o r s t r e n g t h f ( n ' , n ) , a f t e r M e z g e r (1969).
f(n =
8 J , ( s ) J , ' ( s ) n .2
'"> 3 g2 ^ T (n'<n) (3.14)
Here
s = n - n' (3.15)
F o r s = 2, n = 5 ( i . e . 5 3 t r a n s i t i o n ) t h e e r r o r i s 10%
s = l , n = 1 0 ( i : e . 10 9 t r a n s i t i o n ) t h e e r r o r i s 0 . 5 %
a n d f o r t h e r a d i o - r e c o m b i n a t i o n l i n e s it i s n e g l i g i b l e .
E n c o u r a g e d b y t h i s a g r e e m e n t w e c a n c o n t i n u e in t h e s p i r i t of C o p e n h a g e n
and G ö t t i n g e n of t h e 1 9 2 0 s a n d a p p l y t h e c o r r e s p o n d e n c e p r i n c i p l e to
collisions.
4. CLASSICAL COLLISIONS
In t h e c a s e of t h e t h e o r y of r a d i a t i o n , we w e r e a b l e t o a p p e a l to a
s t a n d a r d text f o r the c o r r e s p o n d i n g c l a s s i c a l t h e o r y . F o r collisions this is
not s o , a n d b e f o r e c o n s i d e r i n g t h e c o r r e s p o n d e n c e p r i n c i p l e w e m u s t
d e v e l o p t h e c l a s s i c a l t h e o r y of c o l l i s i o n s . F i r s t c o n s i d e r t h e t h e o r y of
c o l l i s i o n s of c h a r g e d p a r t i c l e s with h i g h l y e x c i t e d a t o m s .
Suppose a c l a s s i c a l e l e c t r o n collides with a c l a s s i c a l H - a t o m with a
n u c l e u s of i n f i n i t e m a s s . U i s t h e b i n d i n g e n e r g y of t h e a t o m w h i c h in t h i s
c l a s s i c a l m o d e l i s not q u a n t i z e d ( i . e . w e h a v e a c o n t i n u u m of b o u n d s t a t e s ) .
IAEA-SMR-12/44, 46 , 48 247
L e t E b e t h e i n i t i a l e n e r g y of t h e i n c i d e n t e l e c t r o n a n d s u p p o s e that
E > U (4.1)
F o r i o n i z a t i o n to t a k e p l a c e , t h e bound e l e c t r o n m u s t gain enough e n e r g y

to l e a v e t h e p r o t o n , but the incident e l e c t r o n m u s t not l o s e so m u c h e n e r g y
t h a t it b e c o m e s bound to the p r o t o n .
We c a n c l a s s i f y c l a s s i c a l c o l l i s i o n s of e l e c t r o n s with H a t o m s a c c o r d i n g
to the r a n g e of v a l u e s of the e n e r g y t r a n s f e r
ДЕ = E - E ' (4.2)
f r o m t h e incident e l e c t r o n to the i n i t i a l l y bound e l e c t r o n . Here E1 is the

f i n a l e n e r g y of t h e incident e l e c t r o n .
We h a v e t h e p o s s i b i l i t i e s :
Direct scattering;
ДЕ < U i n c l u d e s both e x c i t a t i o n (4.3a)
and d e - e x c i t a t i o n
U < ДЕ < E Ionization (4.3b)
E < ДЕ Exchange (4.3c)
T h e exchange p r o c e s s i s m o r e v i o l e n t t h a n the i o n i z a t i o n , but i s v e r y

r a r e when E U.
T h e c l a s s i c a l i o n i z a t i o n c r o s s - s e c t i o n i s given by
<j c = cr c (U < Д Е < E ) (4.4)
T h e q u a n t a l c r o s s - s e c t i o n f o r highly e x c i t e d s t a t e s is given to a good

a p p r o x i m a t i o n by t h e s a m e f o r m u l a
CTq~crc v( 4 . 5 )
i l '
(The e r r o r i s v e r y s m a l l . )
S y s t e m s of p a r t i c l e s i n t e r a c t i n g t h r o u g h Coulomb f o r c e s s a t i s f y s i m p l e
s c a l i n g l a w s . If old t r a j e c t o r i e s R ; (t) f o r 3 - p a r t i c l e s i = 1, 2, 3 s a t i s f y t h e
e q u a t i o n s of m o t i o n , t h e n new t r a j e c t o r i e s RJ(t') a l s o s a t i s f y t h e e q u a t i o n s
of m o t i o n , p r o v i d e d t h a t
R.(t)=6R!(ť) (4.6a)
t = e3/2ť (4.6b)
F o r e x a m p l e , in t h e K e p l e r m o t i o n of a p l a n e t , the p e r i o d v a r i e s a s t h e
3 / 2 p o w e r of t h e r a d i u s of o r b i t . H o w e v e r t h e s c a l i n g law a p p l i e s f o r any
n u m b e r of c h a r g e d p a r t i c l e s . T h i s m a y b e v e r i f i e d by s u b s t i t u t i o n in
N e w t o n ' s e q u a t i o n s of m o t i o n . F o r the s c a l i n g of a c o m p l e x d y n a m i c a l
p r o b l e m , a l l p o s i t i o n s and l e n g t h s m u s t b e s c a l e d a s in (4. 6a) and a l l t i m e s
a s in ( 4 . 6 b ) . V e l o c i t i e s v , e n e r g i e s E a n d c r o s s - s e c t i o n s a r e s c a l e d
a c c o r d i n g to t h e t r a n s f o r m a t i o n s
v = 6"*v' (4.7a)
248 PERCIVAL
E = e"1E' (4.7b)
a (4.7c)
C o n s e q u e n t l y , if our H a t o m h a s the b i n d i n g e n e r g y U, t h e quantity
CT( E/U)/<yg (4.8)
i s a u n i v e r s a l f u n c t i o n of t h e d i m e n s i o n l e s s quantity E / U , w h e r e the g e o -
m e t r i c c r o s s - s e c t i o n is
a S = 7га2 = — g (independent of t h e i n c i d e n t p a r t i c l e ) (4.9)
T h e s c a l i n g l a w s e n a b l e u s to o b t a i n c r o s s - s e c t i o n s f o r a t o m s of a l l
b i n d i n g e n e r g i e s f r o m t h o s e of a given binding e n e r g y , s a y U = \ in s o m e
units.
T h e i n i t i a l c o n d i t i o n s f o r a c l a s s i c a l c o l l i s i o n depend on t h e n a t u r e of
the q u a n t a l c o l l i s i o n that it is hoped to m o d e l . F o r a highly e x c i t e d l e v e l n,
t h e r e a r e m a n y d i f f e r e n t p o s s i b l e c o l l i s i o n s , depending on the d i s t r i b u t i o n
a m o n g the ( n í m ) s t a t e s o f t h a t l e v e l . We n e g l e c t s p i n .
In a s t r o p h y s i c a l s i t u a t i o n s and in l a b o r a t o r y p l a s m a s t h e individual
s t a t e s f o r a given n a r e i n i t i a l l y equally p o p u l a t e d to a v e r y good a p p r o x i -
m a t i o n . T h e d i s t r i b u t i o n with t h e s e p r o p e r t i e s with e n e r g y U n fixed and
( i m ) s t a t e s equally p o p u l a t e d i s known in s t a t i s t i c a l m e c h a n i c s a s a q u a n t a l
microcanonical distribution.
Highly e x c i t e d s t a t e s p r o d u c e d by c o l l i s i o n s e x c i t i n g f r o m the g r o u n d
s t a t e and a l s o by c h a r g e t r a n s f e r have a d i f f e r e n t d i s t r i b u t i o n which i s
u s u a l l y unknown in d e t a i l . F o r this r e a s o n we c o n s i d e r only t h e m i c r o -
canonical distribution.
A c l a s s i c a l m i c r o c a n o n i c a l d i s t r i b u t i o n c o n s i s t s of h y d r o g e n a t o m s with
f i x e d b i n d i n g e n e r g y U, and e l l i p t i c a l e l e c t r o n o r b i t s which a r e d i s t r i b u t e d
i s o t r o p i c a l l y with all o r i e n t a t i o n s , and with a d i s t r i b u t i o n in e c c e n t r i c i t y
which i s u n i f o r m in e 2 b e t w e e n 0 and 1. T h e c l a s s i c a l d i s t r i b u t i o n
c o r r e s p o n d i n g to the q u a n t a l m i c r o c a n o n i c a l d i s t r i b u t i o n at l e v e l n i s
Binding e n e r g y . U = Ry/n2 (4.10a)

2
e u n i f o r m l y d i s t r i b u t e d in (0, 1 ) (4.10b)
A r b i t r a r y orientation, isotropic
(spherically symmetric) distribution (4.10c)
C l a s s i c a l l y one can s p e c i f y position and m o m e n t u m s i m u l t a n e o u s l y ;

q u a n t a l l y , by t h e u n c e r t a i n t y p r i n c i p l e , one c a n n o t . T h u s in m a k i n g a
c l a s s i c a l m o d e l of a q u a n t a l a t o m one cannot at the s a m e t i m e obtain t h e
c o r r e c t d i s t r i b u t i o n in p o s i t i o n and m o m e n t u m of t h e o r b i t i n g e l e c t r o n .
F o r a collision the momentum distribution is much m o r e important
t h a n t h e d i s t r i b u t i o n in p o s i t i o n .
T h e m i c r o c a n o n i c a l q u a n t a l d i s t r i b u t i o n in m o m e n t u m w a s given by
F o c k (1935) a s
(4.11)
IAEA-SMR-12/44,46,48 249
where
pť n = m e vn = 4(2m e Un ' 4 ( 4 . 1 2 )'
By good f o r t u n e t h i s d i s t r i b u t i o n in m o m e n t u m is i d e n t i c a l to the c l a s -
s i c a l m i с r o c ano ni c a l d i s t r i b u t i o n in m o m e n t u m f o r b i n d i n g e n e r g y U n and
f o r a l l n. ( T h i s i s a p r o p e r t y which c o m e s f r o m a c o n s i d e r a t i o n of g r o u p
s y m m e t r i e s . ) T h i s r e m o v e s all doubt as to what i n i t i a l c o n d i t i o n s should
be chosen for the atom - a classical microcanonical distribution over
elliptical orbits.
F o r s i m p l i c i t y of c a l c u l a t i o n , s o m e a u t h o r s e x p l i c i t l y o r i m p l i c i t l y
c o n s i d e r an i n i t i a l i s o t r o p i c d i s t r i b u t i o n of c i r c u l a r o r b i t s (e = 0) f o r which
t h e m o m e n t u m p i s f i x e d in m a g n i t u d e at p n . P a r t i c u l a r l y f o r h i g h - e n e r g y
c o l l i s i o n s t h i s i s in p r a c t i c e a f a i r l y good a p p r o x i m a t i o n f o r t r a n s i t i o n s
between different levels.
5. CLASSICAL CROSS-SECTIONS
T h e r e a r e t h r e e m a i n m e t h o d s which h a v e b e e n u s e d to obtain c l a s s i c a l
c r o s s - s e c t i o n s f o r c o l l i s i o n s b e t w e e n c h a r g e d p a r t i c l e s of m a s s m j and
atoms.
Classical-impulse or binary-encounter approximation (5.1a)

Classical perturbation theory (5.1b)
O r b i t i n t e g r a t i o n o r Monte C a r l o m e t h o d (5.1c)
E a c h of t h e s e m e t h o d s is a p p r o p r i a t e in p a r t i c u l a r c i r c u m s t a n c e s
d e f i n e d by t h e n o r m a l i z e d i n c i d e n t e n e r g y E / U = m e E / m 1 U and t h e n o r m a l i z e d
energy t r a n s f e r Д Е / U . The appropriate ranges a r e
B i n a r y e n c o u n t e r Ë ' » U, ЁДЕ » U2 (5.2a)

Classical perturbation theory ДЕ « U (5.2b)
Monte C a r l o Ë ~ U (5.2c)
T h e a p p r o x i m a t i o n s a r e given in i n c r e a s i n g o r d e r of d i f f i c u l t y . F o r incident
e l e c t r o n s Ê = E a n d f o r incident i o n s , including p r o t o n s , E i s t h e e n e r g y of
a n e l e c t r o n with t h e s a m e v e l o c i t y a s the i n c i d e n t i o n .
T h e b i n a r y - e n c o u n t e r o r c l a s s i c a l - i m p u l s e a p p r o x i m a t i o n h a s a long and
t o r t u o u s h i s t o r y . T h e e x c e l l e n t but v e r y t e r s e l y w r i t t e n e a r l y p a p e r s of
T h o m a s ( 1 9 2 7 a , b ) , W i l l i a m s (1931) and o t h e r s in t h e 1930s w e r e l a r g e l y
f o r g o t t e n d u r i n g t h e b u r s t of e n t h u s i a s m following the p u b l i c a t i o n of
G r y z i n s k i (1959). D e t a i l s can be found in r e v i e w a r t i c l e s ( B u r g e s s and
P e r c i v a l 1968, V r i e n s 1967). T h i s a p p r o x i m a t i o n i s b a s e d on the a s s u m p t i o n
t h a t t h e p r o b a b i l i t y of a given e n e r g y t r a n s f e r Д Е i s the s a m e a s if t h e
i n c i d e n t p a r t i c l e w e r e p a s s i n g t h r o u g h a g a s of f r e e e l e c t r o n s with t h e s a m e
v e l o c i t y d i s t r i b u t i o n a s that of the e l e c t r o n s in the c l a s s i c a l m o d e l a t o m .
S i n c e t h e e n e r g y of a c l a s s i c a l bound s y s t e m i s c o n t i n u o u s , l i k e e v e r y
d y n a m i c a l v a r i a b l e of c l a s s i c a l m e c h a n i c s , t h e c l a s s i c a l c r o s s - s e c t i o n f o r
an e n e r g y t r a n s f e r Д Е i s a d i f f e r e n t i a l c r o s s - s e c t i o n
250 PERCIVAL
эЙз <5-3)
C l a s s i c a l l y , the t o t a l c r o s s - s e c t i o n f o r e n e r g y t r a n s f e r b e t w e e n two l i m i t s
AE mm . a n d A E max i s
AE
max
' ( A E m i l < A E < AEmax) = J ^ dAE (5.4)
AEm .in
The b i n a r y - e n c o u n t e r d i f f e r e n t i a l c r o s s - s e c t i o n is obtained f r o m t h e
R u t h e r f o r d f o r m u l a through the important, deceptively simple, T h o m a s
e x p r e s s i o n f o r the double d i f f e r e n t i a l c r o s s - s e c t i o n 9 2 a / ( 3 q 9 A E ) ,
w h e r e q i s t h e m a g n i t u d e of t h e m o m e n t u m t r a n s f e r . It i s given by
тг 32P _ 4тге2 1
X i s a f u n c t i o n of v 0 , V, q and ЛЕ which i s 1 when t h e s e q u a n t i t i e s a r e

c o n s i s t e n t with c o n s e r v a t i o n conditions and 0 o t h e r w i s e . In t h e T h o m a s
f o r m u l a it i s s u p p o s e d ~J 2E/m1 = V i s t h e velocity of the incident p a r t i c l e
and that t h e bound e l e c t r o n h a s an i s o t r o p i c v e l o c i t y d i s t r i b u t i o n with fixed
m a g n i t u d e v 0 . T h i s would be the c a s e f o r c i r c u l a r o r b i t s .
I n t e g r a t i n g t h i s e x p r e s s i o n o v e r m o m e n t u m t r a n s f e r we o b t a i n f o r t h e
b i n a r y - e n c o u n t e r (BE) i o n i z a t i o n c r o s s - s e c t i o n
i / £ I . 1 _L ^ ( B E ЬУ e l e c t r o n s ) (5.6)
g V 3 " g " 3 g 2 ; (g=E/U)
4 f 5 1 • N, (BE by p r o t o n s )
(5
E V3 4 ( 2 - 1) (Ê = m e E / m U) "7)
A d d i t i o n a l f a c t o r s a r e s o m e t i m e s i n t r o d u c e d to t a k e account of a c c e l e r a t i o n
of the incident p a r t i c l e by the n u c l e u s , n e g l e c t e d in t h e o r i g i n a l a p p r o x i m a -
tion, a n d / o r f o c u s s i n g of i n c i d e n t e l e c t r o n s .
F o r a given i n c i d e n t e n e r g y E , t h i s a p p r o x i m a t i o n i s only v a l i d f o r
s u f f i c i e n t l y l a r g e e n e r g y t r a n s f e r s , by condition ( 5 . 2 a ) .
When t h e c o l l i s i o n i s w e a k e r , the b i n a r y - e n c o u n t e r a p p r o x i m a t i o n
b r e a k s down, but it i s p o s s i b l e to u s e c l a s s i c a l p e r t u r b a t i o n t h e o r y in a
s i m i l a r f a s h i o n to L a g r a n g e ' s t r e a t m e n t of t h e p e r t u r b a t i o n of the p l a n e t s .
T h e w o r k done by t h e p a s s i n g p a r t i c l e , s u p p o s e d to b e u n p e r t u r b e d , on
t h e o r b i t i n g e l e c t r o n i s c a l c u l a t e d by t h e f o r m u l a
CO
ДЕ W = J F 1 2 • d? 2 (5. 8)
Using L a g r a n g e ' s e x p a n s i o n ( 3 . 7 - 3 . 1 0 ) we can obtain a s e r i e s f o r m f o r

AE in t e r m s of t h e F o u r i e r c o m p o n e n t s of t h e m o t i o n and t h e a n g l e s of
o r i e n t a t i o n of t h e e l l i p t i c o r b i t . By a v e r a g i n g o v e r t h e s e o r i e n t a t i o n s and
making some fairly satisfactory simplifying assumptions, the differential
c r o s s - s e c t i o n c a n be obtained in the " a d i a b a t i c " r e g i o n of d i r e c t c o l l i s i o n s
( e x c i t a t i o n and d e - e x c i t a t i o n ) w h e r e t h e b i n a r y - e n c o u n t e r t h e o r y b r e a k s down.
IAEA-SMR-12/44,46,48 251
By c a r e f u l c o n s i d e r a t i o n of d i s t r i b u t i o n s in e n e r g y t r a n s f e r , i m p a c t
p a r a m e t e r and m o m e n t u m t r a n s f e r , it i s p o s s i b l e to obtain a c o m b i n e d
t h e o r y which i s j u s t i f i e d by b i n a r y - e n c o u n t e r and c l a s s i c a l p e r t u r b a t i o n
t h e o r y in t h e i r r e s p e c t i v e r e g i o n s of v a l i d i t y ( P e r c i v a l , 1973b). T h e
r e s u l t a n t c r o s s - s e c t i o n s a r e o b t a i n e d n u m e r i c a l l y but m a y b e a p p r o x i m a t e d
by t h e s i m p l e a n a l y t i c f o r m :
Эст
C(q_) - C(q + ) (AE > 0) (5.9)
ЭДЕ
where
ДЕ
«Û = l § 1 + ± 1 (5.10a)
U
and
Cfx" 1 ) : In 1 + (5.10b)
Unlike both t h e b i n a r y - e n c o u n t e r and c o m b i n e d t h e o r y i s the c l a s s i c a l -

t r a j e c t o r y o r Monte C a r l o m e t h o d which m u s t b e u s e d when the a n a l y t i c
m e t h o d s b r e a k down, p a r t i c u l a r l y when t h e v e l o c i t y of t h e incident p a r t i c l e
i s c o m p a r a b l e to that of the bound e l e c t r o n ( P e r c i v a l , 1973c).
In t h i s m e t h o d the c l a s s i c a l p r o b l e m i s solved d i r e c t l y by r e p e a t e d
n u m e r i c a l i n t e g r a t i o n of the c l a s s i c a l e q u a t i o n s of m o t i o n f o r i n i t i a l s t a t e s
which a r e c h o s e n by a p p r o p r i a t e r a n d o m s a m p l i n g in the s p a c e of p o s i t i o n s
and v e l o c i t i e s of a l l t h r e e c o l l i d i n g p a r t i c l e s . T h i s f o r m s in e f f e c t a
c o m p u t e r m o d e l of t h e p h y s i c a l s c a t t e r i n g p r o c e s s .
о 50 100 150 200 250 300

INCIDENT PROTON ENERGY ( keV)
FIG. 2 . p - H i o n i z a t i o n c r o s s - s e c t i o n for i n i t i a l n = l . Full c u r v e : Bates a n d G r i f f i n g ( 1 9 5 3 ) using Born

approximation; open circles: Gilbody and Ireland (1963); full circles: Fite et a l . ( i 9 6 0 ) ; squares:
Monte Carlo results.
2 5 2 PERCIVAL
T h e c r o s s - s e c t i o n s , both total and d i f f e r e n t i a l , a r e obtained by counting

t h e n u m b e r of f i n a l s t a t e s with p a r a m e t e r s s u c h a s e n e r g y t r a n s f e r , in a
given r a n g e . T h e e r r o r s a r e both s y s t e m a t i c a n d s t a t i s t i c a l . The s y s t e m a t i c
e r r o r s c o m e f r o m the f i n i t e s t e p length of n u m e r i c a l i n t e g r a t i o n and c u t - o f f s
due to f i n i t e t i m e s at which i n t e g r a t i o n m u s t n e c e s s a r i l y s t a r t and f i n i s h and
to t h e finite m a x i m u m i m p a c t p a r a m e t e r . Unlike t h e e x p e r i m e n t a l s i t u a t i o n
" e r r o r p a r a m e t e r s " c a n be c h o s e n w h i c h r e d u c e t h e s y s t e m a t i c e r r o r s to
v a l u e s below t h e s t a t i s t i c a l e r r o r s due to t h e finite s a m p l e . T h e l a t t e r can
b e r e p r e s e n t e d by s t a n d a r d deviation a s in a l a b o r a t o r y e x p e r i m e n t , as f o r
the p - H ionization c u r v e of A b r i n e s a n d P e r c i v a l (1966b), shown in F i g . 2 .
T h e c o m p u t i n g t i m e is long, but not p r o h i b i t i v e , f o r s t a n d a r d e r r o r s
~5% f o r t o t a l c r o s s - s e c t i o n s and ~ 15% f o r s i n g l e d i f f e r e n t i a l c r o s s - s e c t i o n s .
Many of the c l a s s i c a l r e s u l t s w e r e o b t a i n e d f o r a t o m s of low q u a n t u m
n u m b e r w h e r e t h e v a l i d i t y i s in g r e a t e r doubt t h a n f o r highly e x c i t e d a t o m s .
N e v e r t h e l e s s , p a r t i c u l a r l y f o r i o n i z a t i o n and f o r c r o s s - s e c t i o n s n e a r t h e i r
m a x i m u m v a l u e , t h e c l a s s i c a l t h e o r y i s not too b a d , even f o r H with n = 1.
6. D I S C R E T E STATES AND CORRESPONDENCE P R I N C I P L E S
We now c o n s i d e r t h e a p p l i c a t i o n of c l a s s i c a l t h e o r i e s to q u a n t a l s y s t e m s ,
the f i e l d of c o r r e s p o n d e n c e p r i n c i p l e s . F o r bound s t a t e s the c l a s s i c a l
e n e r g y " s p e c t r u m " i s continuous w h e r e a s the q u a n t a l s p e c t r u m i s d i s c r e t e .
T h e c l a s s i c a l d i f f e r e n t i a l c r o s s s e c t i o n Эст/ЭДЕ with r e s p e c t to e n e r g y
t r a n s f e r m u s t b e r e l a t e d to t h e t o t a l q u a n t a l c r o s s - s e c t i o n ст(п - n') f r o m
l e v e l n to l e v e l n' of t h e q u a n t i z e d bound s y s t e m .
If Эст/ЭДЕ v a r i e s by only a s m a l l f r a c t i o n o v e r v a l u e s of ДЕ c o r r e s p o n d i n g
to s e v e r a l n e i g h b o u r i n g f i n a l excited s t a t e s n ' , t h e n t h e r e i s l i t t l e difficulty
in o b t a i n i n g f r o m it u n a m b i g u o u s a p p r o x i m a t e e x c i t a t i o n c r o s s - s e c t i o n s ,
b y a s s u m i n g a s m o o t h d i s t r i b u t i o n a m o n g the f i n a l s t a t e s n 1 , a s shown in
F i g , 3 and a s follows
da i da i ЭДЕ
o(n n' ) : 1 (6.1)
9n' 'эДЕ 6n'
ДЕ
3tr
ЛЕ = 0
ЭДЕ
FIG. 3. E x c i t a t i o n c r o s s - s e c t i o n s a s a f u n c t i o n of e n e r g y d i f f e r e n c e .
IAEA-SMR-12/44,46,48 253
H e r e n i s s u p p o s e d to be fixed, ДЕ i s t h e e n e r g y t r a n s f e r
Д Е = Ry (n" 2 - n ' - 2 ) (6.2)
r e q u i r e d to excite the a t o m f r o m l e v e l n to l e v e l n ' , and
(6.3)
i s t h e m e a n e n e r g y r a n g e b e t w e e n s t a t e s l a b e l l e d by n 1 , o r the i n v e r s e m e a n
d e n s i t y of l e v e l s in t h e n e i g h b o u r h o o d of n ' .
T h e t h e o r e t i c a l condition f o r the v a l i d i t y of t h i s d e n s i t y - o f - s t a t e s
c o r r e s p o n d e n c e p r i n c i p l e i n v o l v e s c l a s s i c a l a c t i o n f u n c t i o n s . In p r a c t i c e
it i s v a l i d when
all n , n \ An » 1 (6.4)
and i s s o m e t i m e s v a l i d even when Д п i s c o m p a r a b l e with unity.

T h e c l a s s i c a l t h e o r y with the d e n s i t y - o f - s t a t e s c o r r e s p o n d e n c e p r i n c i p l e
i s s o m e t i m e s i n a d e q u a t e f o r s m a l l Дп. B e c a u s e of t h e s t r o n g s i n g u l a r i t y in
I Эст/ЭДЕ I at ДЕ = 0, t h e a s s i g n m e n t of the e n e r g y r a n g e i s a m b i g u o u s ; and
e v e n t h e f o r m of t h e c r o s s - s e c t i o n c a n be w r o n g .
F o r s u f f i c i e n t l y high i n c i d e n t - p a r t i c l e e n e r g i e s , t h e B e t h e - B o r n
a p p r o x i m a t i o n i s v a l i d and p r o v i d e s a quantal c r o s s - s e c t i o n which h a s the
form
AlnE + В
cr q (n - n ' ) ЯК (E l a r g e ) (6.5)
E
F o r l a r g e n and Дп t h e l o g a r i t h m i c t e r m i s i n s i g n i f i c a n t , but f o r s m a l l Дп
it m a y be dominant f o r v a l u e s of E of p h y s i c a l i n t e r e s t . H o w e v e r the
c l a s s i c a l r e s u l t s ( 5 . 6 , 5 . 7 ) h a v e no l o g a r i t h m i c t e r m .
T h e a d d i t i o n a l l o g a r i t h m i c t e r m c o m e s f r o m weak c o l l i s i o n s with l a r g e
i m p a c t p a r a m e t e r s , w h e r e the c l a s s i c a l e n e r g y t r a n s f e r r e d to t h e bound
e l e c t r o n i s l e s s than the e n e r g y s p l i t t i n g b e t w e e n t h e s t a t e s . T h e n e i g h -
b o u r i n g e n e r g y s t a t e s a r e t h u s c l a s s i c a l l y i n a c c e s s i b l e . Two c l u e s enable
u s to o v e r c o m e t h i s p r o b l e m : W i l l i a m s (1931) pointed out that c l a s s i c a l
t h e o r y can give a c o r r e c t v a l u e f o r t h e e n e r g y l o s s of c h a r g e d p a r t i c l e s ,
e v e n f o r t h e s e weak c o l l i s i o n s , s o t h a t the m e a n c l a s s i c a l e n e r g y t r a n s f e r
b e h a v e s a s if it w e r e s h a r e d out a m o n g the q u a n t u m - m e c h a n i c a l s t a t e s .
B o h r ' s c o r r e s p o n d e n c e p r i n c i p l e f o r r a d i a t i o n d e a l s with a s i m i l a r
s i t u a t i o n , f o r t h e m e a n e n e r g y l o s s of a c l a s s i c a l r a d i a t i n g e l e c t r o n i s
s h a r e d out a m o n g the q u a n t u m - m e c h a n i c a l s t a t e s . In t h i s c a s e the e n e r g y
t r a n s f e r to e a c h q u a n t a l s t a t e i s d e t e r m i n e d by the F o u r i e r c o m p o n e n t s
of t h e i n t e r a c t i o n with t h e r a d i a t i o n f i e l d . T h u s we should e x p e c t t h e
(n -» n 1 ) - t r a n s i t i o n p r o b a b i l i t y P(b) a s a function of the i m p a c t p a r a m e t e r b to
b e r e l a t e d to t h e F o u r i e r c o m p o n e n t s (3.7) of o r d e r s and - s , w h e r e s = n ' - n.
T h i s i s c o r r e c t ( P e r c i v a l and R i c h a r d s , 1 9 7 0 a , b ) p r o v i d e d that t h e i n t e r a c t i o n
i s s u f f i c i e n t l y weak f o r t h e s u m o v e r a l l p r o b a b i l i t i e s f r o m an i n i t i a l s t a t e n
i s s m a l l c o m p a r e d to 1 and p r o v i d e d that j s J <iC n. T h e s e c o n d i t i o n s m e a n
that f i r s t - o r d e r q u a n t a l p e r t u r b a t i o n t h e o r y m u s t b e v a l i d f o r the q u a n t a l
i n t e r a c t i o n and a l s o t h a t c l a s s i c a l p e r t u r b a t i o n t h e o r y m u s t be v a l i d f o r the
classical interaction. Unfortunately this is very r e s t r i c t i v e .
254 PERCIVAL
H e i s e n b e r g (1949) o b t a i n e d a f o r m of t h e c o r r e s p o n d e n c e p r i n c i p l e
which i s m o r e p o w e r f u l and convenient t h a n t h a t of B o h r , and r e l a t e s
c l a s s i c a l F o u r i e r c o e f f i c i e n t s to quantal m a t r i x e l e m e n t s . Suppose
(6.6)
i s t h e p o s i t i o n of a p a r t i c l e moving p e r i o d i c a l l y in one d i m e n s i o n . T h e n
any f u n c t i o n F c (x) m a y a l s o b e e x p r e s s e d a s a F o u r i e r s e r i e s in t i m e :
(6.7)
T h e n H e i s e n b e r g 1 s f o r m of t h e c o r r e s p o n d e n c e p r i n c i p l e s t a t e s that the
q u a n t a l m a t r i x e l e m e n t s b e t w e e n s t a t e s n and n 1 of the d y n a m i c a l v a r i a b l e F
t e n d s to c o i n c i d e with t h e c l a s s i c a l F o u r i e r c o m p o n e n t s
<n' | F | n > «=F°, (s = n - n ' , s « n, n ' ) (6.8)
w h e r e the c l a s s i c a l o r b i t i s t a k e n n e a r the m e a n e n e r g y of t h e i n i t i a l and

f i n a l s t a t e s . The t h e o r y c a n b e g e n e r a l i z e d to s e p a r a b l e s y s t e m s of many
d i m e n s i o n s by u s i n g the t h e o r y of a c t i o n - a n g l e v a r i a b l e s .
T h u s , if a c o l l i s i o n p r o b l e m can b e f o r m u l a t e d in t e r m s of m a t r i x
e l e m e n t s of o p e r a t o r s which a r e known f u n c t i o n s of p o s i t i o n , H e i s e n b e r g ' s
f o r m of t h e c o r r e s p o n d e n c e p r i n c i p l e can b e u s e d .
T h i s t h e o r y , when a p p l i e d to a c l a s s i c a l - p a t h f i r s t - o r d e r q u a n t a l
p e r t u r b a t i o n t h e o r y of c o l l i s i o n s , gives the s a m e r e s u l t a s the a p p l i c a t i o n
of B o h r ' s c o r r e s p o n d e n c e p r i n c i p l e . It h a s a l s o b e e n a p p l i e d to t h e p l a n e -
wave B o r n a p p r o x i m a t i o n by R i c h a r d s (1973) and t o t h e s u d d e n a p p r o x i m a t i o n
( A l d e r , W i n t h e r , 1960; K r a m e r , B e r n s t e i n , 1964) by P e r c i v a l a n d
R i c h a r d s (1970b). T h e l a s t a u t h o r s a l s o d e r i v e d a m o r e g e n e r a l s t r o n g -
c o u p l i n g c o r r e s p o n d e n c e p r i n c i p l e f o r t h e S - m a t r i x v a l i d wherfever f i r s t -
o r d e r c l a s s i c a l perturbation theory is valid for the c l a s s i c a l model. This
l a s t r e s u l t h a s b e e n shown t o a g r e e with t h e d e n s i t y - o f - s t a t e s c o r r e s p o n d e n c e
p r i n c i p l e in the r a n g e 1 « | n - n' | < n, n ' .
T h e t r a n s i t i o n a m p l i t u d e s f o r a o n e - d i m e n s i o n a l s y s t e m f o r weak
coupling, sudden and s t r o n g coupling t h e o r i e s a r e given by
2тг/ш
(6.9)
n'
27Г/ÜJ
( s I « n , n ' ; íú X ( t i m e of c o l l i s i o n ) « 1
) (6.10)
IAEA-SMR-12/44,46,48 255
2тг/ш
S. (n',n)=^~ / dT exp isuT - - / dtV (x(t + t ) , t)
strong v ' 2тг J
о
s с n, n (6.11)
T h e f u n c t i o n V c (x(t + T ) , t ) is the v a l u e of the c l a s s i c a l i n t e r a c t i o n

p o t e n t i a l at t i m e t , w h e r e it i s s u p p o s e d that at t i m e t = 0 t h e bound p a r t i c l e
h a s r e a c h e d the point on i t s o r b i t which i s a t t a i n e d a f t e r a t i m e т f r o m a
given f i x e d i n i t i a l p o i n t . T h e m a n y - d i m e n s i o n a l t h e o r y i s m o r e c o m p l i c a t e d ,
but d i f f e r s in no e s s e n t i a l s .
T h e s e m e t h o d s h a v e b e e n u s e d in a s e r i e s of p a p e r s (the l a s t b e i n g
P e r c i v a l and R i c h a r d s , 1971) to obtain an a n a l y t i c f o r m u l a f o r c o l l i s i o n
c r o s s - s e c t i o n s b e t w e e n e l e c t r o n s and highly e x c i t e d h y d r o g e n a t o m s f o r
i n c i d e n t e l e c t r o n e n e r g i e s E in t h e r a n g e
R
y < E < 1 Ry (6.12)
Above E = 1 Ry t h e B o r n a p p r o x i m a t i o n i s v a l i d , and f o r E in the r a n g e
(6.13)
n2 n
t h e c o r r e s p o n d e n c e - p r i n c i p l e m e t h o d s h a v e b e e n u s e d m o r e r e c e n t l y by
Richards.
B e l o w t h e l o w e r l i m i t of 4 R y / n 2 of E it i s n e c e s s a r y to u s e c l a s s i c a l
Monte C a r l o m e t h o d s .
A n a l y t i c f o r m u l a s a r e a l s o p r o v i d e d f o r incident p o s i t i v e ions and a l s o
f o r t a r g e t s which a r e h y d r o g e n - l i k e i o n s .
7. DISCUSSION O F L I T E R A T U R E
T h e l i t e r a t u r e on highly e x c i t e d s t a t e s i s e x t e n s i v e and h a s not to m y

knowledge b e e n s u m m a r i z e d in a single r e v i e w . H e r e I n a m e a few p a p e r s
c l o s e l y r e l a t e d to t h e t h e m e of c l a s s i c a l and c o r r e s p o n d e n c e m e t h o d s
p r e s e n t e d in t h e s e l e c t u r e s . P u r e l y c l a s s i c a l m e t h o d s and in p a r t i c u l a r
b i n a r y - e n c o u n t e r m e t h o d s h a v e b e e n r e v i e w e d by B u r g e s s and P e r c i v a l
(1968) by V r i e n s (1969) and by B a t e s a n d K i n g s t o n (1970). T h e a u t h o r s w e r e
m a i n l y c o n c e r n e d with t h e a p p l i c a t i o n of t h e t h e o r y to low s t a t e s of a t o m s .
Monte C a r l o m e t h o d s h a v e b e e n a p p l i e d to e l e c t r o n - h y d r o g e n c o l l i s i o n s
by A b r i n e s , P e r c i v a l and V a l e n t i n e (1966), B r a t t s e v and O c h k u r (1967),
M a n s b a c h a n d Keck (1969), P e r c i v a l (1973a) and G r u j i č (1973).
T h e c l a s s i c a l - m e c h a n i c s b a c k g r o u n d to t h e c l a s s i c a l p e r t u r b a t i o n
t h e o r y and t h e c o r r e s p o n d e n c e - p r i n c i p l e m e t h o d s i s b e t t e r p r e s e n t e d by
B o r n (196 0) than in m o s t m o d e r n t e x t s .
A s e m i - c l a s s i c a l t h e o r y of B e i g m a n et a l . (1970), and a s i m p l i f i c a t i o n
of an a p p r o x i m a t e q u a n t a l t h e o r y of P r e s n y a k o v and Urnov (1970) have
both b e e n shown by R i c h a r d s (1972) t o b e equivalent to t h e s t r o n g coupling
correspondence principle f o r one-dimensional motion.
256 PERCIVAL
S a r a p h (1969) h a s a p p l i e d S e a t o n ' s (1962) c l a s s i c a l - p a t h dipole t h e o r y ,

in w h i c h the i n t e r a c t i o n i s t r e a t e d by q u a n t a l p e r t u r b a t i o n t h e o r y o r the
c o n s e r v a t i o n l i m i t , to e l e c t r o n - h y d r o g e n n ^ n + 1 t r a n s i t i o n s . T h e
c o r r e s p o n d e n c e - p r i n c i p l e r e s u l t s a r e in r e a s o n a b l e a g r e e m e n t with t h i s
t h e o r y except f o r the l o w e r incident e n e r g i e s E ,
B o r n o r B e t h e - B o r n c a l c u l a t i o n s h a v e b e e n p e r f o r m e d by McCoyd and
M i l f o r d (1963) by O m i d v a r (1965) and by O m i d v a r and K h a t e e b (1973).
F u r t h e r t h e o r y h a s b e e n p r e s e n t e d by M i n a e v a , S o b e l ' m a n and Sorochenko
(1967). A g e n e r a l r e v i e w of c o l l i s i o n s of c h a r g e of p a r t i c l e s with highly
e x c i t e d s t a t e s i s to a p p e a r ( P e r c i v a l a n d R i c h a r d s , 1975).
A 1971 S u m m e r School P r o c e e d i n g s ( C a r s o n and R o b e r t s , 1972) c o n t a i n s
a r t i c l e s by C h u r c h w e l l , P e r c i v a l and Seaton on the a s t r o p h y s i c a l a s p e c t s
of highly e x c i t e d s t a t e s , and B e r k n e r , King and R i v i e r e (1967) w r i t e on t h e i r
r e l e v a n c e to c o n t r o l l e d t h e r m o n u c l e a r r e a c t i o n s .
T h e r e i s an A p p e n d i x on p h a s e - s p a c e c o n s i d e r a t i o n s a t t a c h e d to t h i s
paper.
ACKNOWLEDGEMENTS
I a m g r a t e f u l to N. P o m p h r e y f o r a s s i s t a n c e in w r i t i n g t h e s e l e c t u r e
n o t e s and to D. R i c h a r d s f o r sending m e h i s p a p e r s b e f o r e p u b l i c a t i o n .
APPENDIX
PHASE SPACE CONSIDERATIONS
T h e p r o p e r t i e s of a q u a n t a l e n e r g y s p e c t r u m in t h e s e m i - c l a s s i c a l l i m i t
of high q u a n t u m n u m b e r s m a y be obtained by t h e m e t h o d s of t h e old q u a n t u m
theory.
A c o n s e r v a t i v e c l a s s i c a l d y n a m i c a l s y s t e m of N d e g r e e s of f r e e d o m i s
i n t e g r a b l e if t h e r e a r e N independent c o n s t a n t s of m o t i o n . A s y s t e m with
e q u a t i o n s of m o t i o n w h i c h a r e c o m p l e t e l y s e p a r a b l e i s a s p e c i a l c a s e .
A c c o r d i n g to a w e l l - k n o w n t h e o r e m of K o l m o g o r o v , A r n o l d and M o z e r ,
bounded s y s t e m s which have an a n a l y t i c H a m i l t o n i a n , and which a r e
s u f f i c i e n t l y c l o s e to b e i n g s e p a r a b l e , have a s i g n i f i c a n t f r a c t i o n of t h e i r
p h a s e s p a c e f u l l of t r a j e c t o r i e s which b e h a v e v e r y m u c h like t h o s e of
s e p a r a b l e s y s t e m s . We s h a l l c a l l the r e g i o n s containing t h e s e t r a j e c t o r i e s
the r e g u l a r r e g i o n s of p h a s e s p a c e .
In r e g u l a r r e g i o n s the t r a j e c t o r i e s lie on N - d i m e n s i o n a l i n v a r i a n t
t o r o i d s . On e a c h t o r o i d t h e r e is defined a v e c t o r a c t i o n c o n s t a n t
I = (I. I * . . . . I N ) (1)
where
I = £ p.dq (2)
bk
and w h e r e q and p a r e a c a n o n i c a l l y c o n j u g a t e v e c t o r c o - o r d i n a t e and

momentum
IAEA-SMR-12/44,46,48 257
q = ( q r q 2 , • . . , q N ); p = (pr p 2 , • • -, p N ) (3)
f o r t h e s y s t e m . T h e b k a r e N independent c l o s e d c u r v e s on the t o r o i d .
E a c h t o r o i d m a y be p a r a m e t r i z e d by the v e c t o r angle v a r i a b l e в, so t h a t
q =QI(0), P = PÏ (0) (4)
E a c h component 0 k of в i s p e r i o d i c of p e r i o d 2u and i s l i n e a r l y
dependent on t h e t i m e t with an ( a n g u l a r ) f r e q u e n c y c o e f f i c i e n t u k
ek = u k t + el (5)
uk = u k ( I ) (6)
T h e c l a s s i c a l m o t i o n r e s o n a t e s in N f u n d a m e n t a l m o d e s of f r e q u e n c i e s u k ,
and a l s o in i n t e g e r c o m b i n a t i o n s of t h e s e f u n d a m e n t a l f r e q u e n c i e s . T h e
m o t i o n i s a l m o s t p e r i o d i c , with an i n f i n i t e n u m b e r of d i s c r e t e F o u r i e r
c o m p o n e n t s . With a r e a s o n a b l e choice of 6 k the a m p l i t u d e s of the o v e r t o n e s
and i n t e r c o m b i n a t i o n m o d e s d e c r e a s e r a p i d l y with t h e i r o r d e r . T h e
s y s t e m r e s o n a t e s s t r o n g l y at r e l a t i v e l y few d i s c r e t e f r e q u e n c i e s .
N u m e r i c a l e x p e r i m e n t s on n o n - i n t e g r a b l e s y s t e m s c l e a r l y show r e g u l a r
r e g i o n s of p h a s e s p a c e . In the 2 - d i m e n s i o n a l cubic p o t e n t i a l w e l l of Hénon
and H e i l e s t h e s y s t e m i s c l o s e to b e i n g i n t e g r a b l e n e a r t h e b o t t o m of t h e
well at E = 0, and t h e r e is an e n e r g y of e s c a p e at E = 1 / 6 . R e g u l a r r e g i o n s
d o m i n a t e t h e p h a s e s p a c e up to E = 1 / 1 2 , w h e r e " i r r e g u l a r " r e g i o n s b e c o m e
s i g n i f i c a n t . T h e i r r e g u l a r r e g i o n s d o m i n a t e n e a r the e s c a p e e n e r g y .
T h e t r a j e c t o r i e s in an i r r e g u l a r r e g i o n a p p e a r to b e h a v e e r g o d i c a l l y
in that r e g i o n . A c c o r d i n g to Contopoulos the i r r e g u l a r r e g i o n s a r e
a s s o c i a t e d with u n s t a b l e o r b i t s . A c c o r d i n g to Sinai, who p r o v e d e r g o d i c i t y
f o r h a r d s p h e r e s , e r g o d i c i t y follows f r o m i n s t a b i l i t y , and so we s h a l l
a s s u m e , in the a b s e n c e of a p r o o f , t h a t t h e t r a j e c t o r i e s in the i r r e g u l a r
r e g i o n s a r e e r g o d i c . A l m o s t e v e r y t r a j e c t o r y q(t), p(t) in an i r r e g u l a r
r e g i o n then h a s a continuous f r e q u e n c y s p e c t r u m and r e a c h e s a r b i t r a r i l y
c l o s e to e v e r y p h a s e point of the s a m e e n e r g y in that i r r e g u l a r r e g i o n . An
i r r e g u l a r r e g i o n h a s t h e d i m e n s i o n 2N.
T h e r e g u l a r and i r r e g u l a r r e g i o n s t h e m s e l v e s have a v e r y c o m p l i c a t e d
g e o m e t r i c a l fine s t r u c t u r e , which we i g n o r e , a s no s t r u c t u r e in a v o l u m e
of p h a s e s p a c e s m a l l e r than (27rh) i s of g r e a t i m p o r t a n c e f o r the q u a n t i z e d
system.
On a p p l y i n g weak t i m e - d e p e n d e n t p e r t u r b a t i o n s to a s y s t e m with a p h a s e
point in a r e g u l a r r e g i o n , the s y s t e m r e s p o n d s at i t s r e s o n a n t m o d a l
f r e q u e n c i e s , with d e c r e a s i n g e f f e c t as t h e o r d e r of the r e s o n a n c e i n c r e a s e s .
A f t e r a weak s h o r t - l i v e d p e r t u r b a t i o n h a s c e a s e d , the new t r a j e c t o r y
a l m o s t a l w a y s s t a y s in the n e i g h b o u r h o o d of the old o n e .
If the s y s t e m w e r e on an i r r e g u l a r t r a j e c t o r y , it would r e s p o n d o v e r a
continuous r a n g e of f r e q u e n c i e s and r a p i d l y d i v e r g e f r o m i t s o r i g i n a l
trajectory.
F r o m the c o r r e s p o n d e n c e p r i n c i p l e it f o l l o w s that a high q u a n t u m l e v e l
of the d i s c r e t e e n e r g y s p e c t r u m of a b o u n d q u a n t a l s y s t e m b e l o n g s to
e i t h e r R, a r e g u l a r e n e r g y s p e c t r u m ,
o r I, a n i r r e g u l a r e n e r g y s p e c t r u m .
258 PÉROVAL
T h e r e g u l a r e n e r g y s p e c t r u m and i t s a s s o c i a t e d s t a t e s h a v e t h e
following p r o p e r t i e s :
( R I ) A s t a t e m a y be l a b e l l e d by the v e c t o r q u a n t u m n u m b e r
n = (n a , n 2 , . . . , n N ) .
(R2) A q u a n t a l s t a t e with quantum n u m b e r n c o r r e s p o n d s to t h o s e p h a s e
s p a c e t r a j e c t o r i e s of t h e c o r r e s p o n d i n g c l a s s i c a l s y s t e m which lie in an
N - d i m e n s i o n a l i n v a r i a n t t o r o i d with a c t i o n c o n s t a n t s I k given by q u a n t u m
c o n d i t i o n s of t h e B o h r - S o m m e r f e l d - W i l s o n t y p e :
I k = (n k + c o n s t a n t ) h
A p a r t f r o m the p h a s e s p a c e f o r m u l a t i o n and the p o s s i b i l i t y of a n o n - z e r o

c o n s t a n t ( K e l l e r ) t h i s r e s u l t i s due to E i n s t e i n .
(R3) T h e q u a n t a l s t a t e m u s t r e s o n a t e at f r e q u e n c i e s c l o s e to t h o s e of t h e
c o r r e s p o n d i n g c l a s s i c a l m o t i o n . Given two q u a n t a l s t a t e s with one n k
d i f f e r i n g by unity and the o t h e r s the s a m e , t h e P l a n c k r e l a t i o n f o r t h e i r
energy difference is
ДЕк = îiuk (7)
w h e r e u k is a f u n d a m e n t a l f r e q u e n c y on t h e c o r r e s p o n d i n g t o r o i d .
(R4) A " n e i g h b o u r i n g s t a t e " t o a state n° with e n e r g y E ° i s a s t a t e with
v e c t o r q u a n t u m n u m b e r n c l o s e to n . N e i g h b o u r i n g s t a t e s a r e c l o s e in
e n e r g y t o E°, with e n e r g y d i f f e r e n c e no m o r e than a s m a l l m u l t i p l e of t h e
maximum | д Е к | .
(R5) We now u s e t h e c o r r e s p o n d e n c e p r i n c i p l e f o r weak p e r t u r b a t i o n s , whose
m o s t w e l l - k n o w n f o r m i s t h e c o r r e s p o n d e n c e p r i n c i p l e f o r i n t e n s i t y of
r a d i a t i o n . Under weak e x t e r n a l p e r t u r b a t i o n s t h e s t a t e n° i s m u c h m o r e
s t r o n g l y coupled to n e i g h b o u r i n g s t a t e s t h a n to o t h e r s t a t e s , with the
coupling tending to d e c r e a s e r a p i d l y with | n - n°| .
Not a l l s t a t e s c l o s e in e n e r g y to a given s t a t e a r e n e i g h b o u r i n g s t a t e s ,
not e v e n all t h o s e belonging to t h e s a m e r e g u l a r s p e c t r u m . H o w e v e r ,
e x p e r i m e n t s which a r e a b l e to select a few h i g h - n s t a t e s of a r e g u l a r
s p e c t r u m have a high p r o b a b i l i t y of s e l e c t i n g n e i g h b o u r i n g s t a t e s , so it
would be p o s s i b l e t o o b s e r v e t h e r e g u l a r i t y . If t r a n s i t i o n s with e n e r g y
d i f f e r e n c e s Д Е 1 a n d Д Е 2 a r e o b s e r v e d , a p p r o x i m a t e m u l t i p l e s and i n t e g e r
c o m b i n a t i o n s of t h e m would a l s o be o b s e r v a b l e . Bound i n t e g r a b l e s y s t e m s
have a regular s p e c t r u m .
T h e c o r r e s p o n d e n c e p r i n c i p l e p r e d i c t s p r o p e r t i e s of an i r r e g u l a r
s p e c t r u m in s t r i k i n g c o n t r a s t to t h o s e of a r e g u l a r s p e c t r u m :
(11) T h e r e i s no u n a m b i g u o u s a s s i g n m e n t of a v e c t o r q u a n t u m n u m b e r to a
s t a t e фQ.
(12) T h e d i s c r e t e bound s t a t e quantal s p e c t r u m m u s t tend to a continuous
c l a s s i c a l s p e c t r u m in t h e c l a s s i c a l l i m i t . T h e e n e r g y d i f f e r e n c e s
Е(ф) - E((//0) = (8)
f o r fixed s t a t i o n a r y s t a t e ф0 a n d v a r y i n g ф f o r m a d i s c r e t e d i s t r i b u t i o n which
t e n d s to t h e continuous d i s t r i b u t i o n i n t i ú .
(13) T h e e n e r g y d i f f e r e n c e s c a n have l i t t l e s t r u c t u r e — t h e d i s t r i b u t i o n of
l e v e l s at t h e i r r e g u l a r s p e c t r u m would a p p e a r to b e a r a n d o m d i s t r i b u t i o n
c o n s i s t e n t with (12).
IAEA-SMR-12/44,46,48 2 5 9
(14) B y a p p l y i n g t h e c o r r e s p o n d e n c e p r i n c i p l e f o r weak p e r t u r b a t i o n s , t h e r e
a r e no n e i g h b o u r i n g s t a t e s in the s e n s e of (R4) and (R5). E x c e p t f o r
s e l e c t i o n r u l e s and a c c i d e n t s , a s t a t e of an i r r e g u l a r s p e c t r u m i s coupled by
a weak p e r t u r b a t i o n with i n t e n s i t i e s of s i m i l a r m a g n i t u d e to all t h o s e
s t a t e s of a s i m i l a r e n e r g y which c o r r e s p o n d to the s a m e i r r e g u l a r r e g i o n of
c l a s s i c a l p h a s e s p a c e . The n u m b e r of s u c h s t a t e s i s v e r y l a r g e , of o r d e r
where nj is a typical quantum number,

(15) T h e e n e r g i e s of t h e i r r e g u l a r s p e c t r u m a r e m o r e s e n s i t i v e to a slowly
changing o r f i x e d p e r t u r b a t i o n t h a n t h o s e of the r e g u l a r s p e c t r u m .
In t h e B o h r - O p p e n h e i m e r a p p r o x i m a t i o n , t h e v i b r a t i o n a l e n e r g y
s p e c t r u m of a p o l y a t o m i c m o l e c u l e i s o b s e r v e d to b e r e g u l a r n e a r e q u i l i -
b r i u m , except f o r F e r m i r e s o n a n c e s , which a r e a r e s i d u a l f o r m of i r r e g u l a r
s p e c t r u m . N e a r the d i s s o c i a t i o n l i m i t the s p e c t r u m should be m a i n l y
i r r e g u l a r , with a l a r g e n u m b e r of w e a k e m i s s i o n l i n e s in p l a c e of a s m a l l
n u m b e r of s t r o n g o n e s . A r e g u l a r p r o g r e s s i o n should b e o b s e r v e d to
t e r m i n a t e a b r u p t l y at a m a x i m u m e n e r g y below the d i s s o c i a t i o n l i m i t . An
i r r e g u l a r s p e c t r u m could e a s i l y b e c o n f u s e d with a c o n t i n u u m u n d e r poor
c o n d i t i o n s of o b s e r v a t i o n .
P r e c i s e c a l c u l a t i o n s on a n i r r e g u l a r s p e c t r u m would b e difficult to
c a r r y out, e v e n with a c o m p l e t e knowledge of the i n t e r a c t i o n . If s t r o n g
i n t e r a c t i o n s a r e b a s i c a l l y n o n - l i n e a r t h e s a m e would apply to t h e h i g h e r
r e s o n a n c e s of p a r t i c l e p h y s i c s .
I should like to thank t h e U . K . S c i e n c e R e s e a r c h C o u n c i l f o r a g r a n t ,
the I n t e r n a t i o n a l C e n t r e f o r T h e o r e t i c a l P h y s i c s f o r t h e i r h o s p i t a l i t y and
Neil P o m p h r e y for a helpful discussion.
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l A E A - S M R - 1 2 / 4 4 , 4 6 , 48
ASTROPHYSICAL APPLICATIONS
OF ATOMIC PHYSICS
M.J. SEATON
Department of Physics and Astronomy,
University College, London,
United Kingdom
Abstract
ASTROPHYSICAL APPLICATION OF A T O M I C PHYSICS.

In t h r e e s e c t i o n s t h e a u t h o r discusses t h e i n f o r m a t i o n w h i c h c a n b e d e d u c e d f r o m t h e r a d i a t i o n e m i t t e d by:
1. Stellar atmospheres; 2. T h e solar c o r o n a ; 3. Gaseous n e b u l a e .
INTRODUCTION
The s t e l l a r a t m o s p h e r e s , the s o l a r c o r o n a , and the g a s e o u s nebulae,

a r e c o n s i d e r e d in t h r e e s e c t i o n s .
In o r d e r t o a p p r e c i a t e t h e p r o b l e m s in a t o m i c p h y s i c s w h i c h a r e of
i m p o r t a n c e f o r a s t r o p h y s i c s , it i s n e c e s s a r y to h a v e s o m e k n o w l e d g e of
the g e n e r a l n a t u r e of the a s t r o n o m i c a l p h e n o m e n a c o n c e r n e d . In p r e p a r i n g
w r i t t e n n o t e s t h e a u t h o r h a s c o n c e n t r a t e d a t t e n t i o n on the g e n e r a l n a t u r e
of t h e a s t r o n o m i c a l p r o b l e m s .
A s b a c k g r o u n d m a t e r i a l t h e f o l l o w i n g g e n e r a l r e f e r e n c e s s h o u l d be
m e n t i o n e d . F o r a n i n t r o d u c t i o n to a s t r o n o m y , " D e r n e u e K o s m o s " by
A. Unsold, H e i d e l b e r g e r T a s c h e n b ü c h e r , Band 16/17 (English T r a n s l a t i o n ,
" T h e New C o s m o s " , L o n g m a n s , 1969), c a n be r e c o m m e n d e d . A S u m m e r
S c h o o l a t S t i r l i n g i n 1971 w a s c o n c e r n e d w i t h " A t o m s and M o l e c u l e s i n
A s t r o p h y s i c s " (edited b y T . R . C a r s o n and M . J . R o b e r t s and p u b l i s h e d
by A c a d e m i c P r e s s , 1972). A v a l u a b l e r e c e n t r e v i e w a r t i c l e i s :
V . M . M y e r s c o u g h and G . P e a c h , " A t o m i c P r o c e s s e s i n A s t r o p h y s i c a l
P l a s m a s " , ( C a s e S t u d i e s i n A t o m i c C o l l i s i o n P h y s i c s , V o l . 2 , 1972; "
E d s M . R . C . M c D o w e l l and E . W . M c D a n i e l , N o r t h - H o l l a n d P u b l . )
T h e a u t h o r h i m s e l f a l s o g a v e s o m e l e c t u r e s on " P r o b l e m s in A s t r o -
p h y s i c s " — w i t h e m p h a s i s o n a t o m i c p r o c e s s e s — at t h e B o u l d e r I n s t i t u t e
f o r T h e o r e t i c a l P h y s i c s , 1961 ( e d i t e d b y W . E . B r i t t i n , B . W . D o w n s and
J . D o w n s , a n d p u b l i s h e d by I n t e r s c i e n c e , 1962).
M a n y t o p i c s i n a t o m i c p h y s i c s r e l e v a n t to a s t r o p h y s i c s a r e d i s c u s s e d
in " P l a s m a S p e c t r o s c o p y " by H . R . G r i e m , M c G r a w H i l l , 1964.
1. STELLAR ATMOSPHERES
A p h o t o n p r o d u c e d i n t h e i n t e r i o r of a s t a r h a s only a v e r y s m a l l
p r o b a b i l i t y of e s c a p i n g f r o m t h e s t a r . P u t a n o t h e r w a y , t h e r a d i a t i o n
w h i c h we o b s e r v e f r o m a s t a r c o m e s f r o m a t h i n o u t e r l a y e r . T h i s o b s e r v a -
b l e r e g i o n i s known a s t h e s t e l l a r a t m o s p h e r e . L e t t h e a t m o s p h e r e h a v e
a t h i c k n e s s A r and t h e s t a r a r a d i u s R s . We u s u a l l y h a v e A r « R s , in
w h i c h c a s e w e can n e g l e c t e f f e c t s of c u r v a t u r e , a n d d i s c u s s t h e a t m o s p h e r e
2 6 1
262 SEATON
in a p l a n e p a r a l l e l a p p r o x i m a t i o n . L e t the s t a r have a m a s s M*s. T h e

g r a v i t a t i o n a l f o r c e , p e r unit m a s s , in the a t m o s p h e r e i s g = G M S / R 2 . TO
a v e r y good a p p r o x i m a t i o n , t h e g r a v i t a t i o n a l f o r c e m u s t b a l a n c e t h e p r e s s u r e
gradient, i . e .
^ = - P < Dg (1.1)
w h e r e : r i s a d i s t a n c e m e a s u r e d o u t w a r d s in a d i r e c t i o n at r i g h t a n g l e s
to t h e p l a n e p a r a l l e l l a y e r s of the a t m o s p h e r e ; p ( r ) i s the p r e s s u r e ; p(r)
i s the density.
C o l l i s i o n s a r e a l w a y s v e r y e f f e c t i v e in r e - d i s t r i b u t i n g k i n e t i c e n e r g y
and in s e t t i n g up a Maxwell d i s t r i b u t i o n of p a r t i c l e v e l o c i t i e s . We m a y
t h e r e f o r e a s s u m e t h a t t h e c o n c e p t of a l o c a l kinetic t e m p e r t u r e , T ( r ) , i s
w e l l d e f i n e d . We m a y a l s o a s s u m e the p e r f e c t g a s law, p = NkT w h e r e
N i s t h e t o t a l n u m b e r of p a r t i c l e s p e r unit v o l u m e . We m a y put p = Npi
w h e r e ß i s t h e m e a n m o l e c u l a r w e i g h t . T h e equation of s t a t e i s t h e n
P = ркТ/м (1.2)
T h e c o n d i t i o n s in the a t m o s p h e r e a r e f u r t h e r d e t e r m i n e d by t h e f a c t
t h a t e n e r g y i s p r o d u c e d in t h e i n t e r i o r of t h e s t a r , p a s s e s t h r o u g h t h e
a t m o s p h e r e , and i s r a d i a t e d into s p a c e . L e t I„ dy du ds_^be the r a d i a n t
e n e r g y p e r unit t i m e c r o s s i n g an a r e a d s in a d i r e c t i o n t n o r m a l to d s ,
and within a solid angle du and f r e q u e n c y r a n g e dy. In going a d i s t a n c e àî.,
e n e r g y c a n be both a b s o r b e d and e m i t t e d . T h e e q u a t i o n of r a d i a t i v e t r a n s f e r
is
^ f = - p * u l v +PÍV (1.3a)
w h e r e kv i s the a b s o r p t i o n c o e f f i c i e n t p e r unit m a s s , and j ^ t h e e m i s s i v i t y

p e r unit m a s s , and p e r unit solid a n g l e . L e t the d i r e c t i o n SL m a k e an angle
0 with t h e d i r e c t i o n ? . We t h e n have d r = c o s 9 di and t h e t r a n s f e r equation
= - p »c„ I„ +piv (1.3b)
It m a y be a s s u m e d t h a t kv and depend only on r ; I v , h o w e v e r , d e p e n d s

on both r and 0. T h e t r a n s f e r equation m u s t be solved s u b j e c t to t h e b o u n d a r y
condition t h a t , at t h e top of t h e a t m o s p h e r e , all r a d i a t i o n i s in the o u t w a r d
d i r e c t i o n (we m a y n e g l e c t r a d i a t i o n c o m i n g f r o m s p a c e to the s t a r ) .
T h e o u t w a r d d i r e c t i o n i s 0 < тг/2, the i n w a r d d i r e c t i o n 0 > 7t/2. T h e
b o u n d a r y condition i s I ( r , 0)-> 0 a s r-> » f o r 0 > 7T/2.
T h e i n t e n s i t y I ( r , 6 ) h a s a c o m p o n e n t lv(r,9) cos 6 in the upward direction.
T h e net u p w a r d flux at f r e q u e n c y v i s
F ( r ) = J J lv(r, в) c o s 0 du dv = 2тгJ J I„(r, 0) c o s 0 s i n 0 d6 dv (1.4a)

v=0 6=0
If o t h e r f o r m s of e n e r g y t r a n s f e r , such a s conduction and c o n v e c t i o n , c a n

b e n e g l e c t e d , e n e r g y c o n s e r v a t i o n r e q u i r e s that
I A E A - S M R - 1 2 / 4 4 , 46 , 4 8 263
F = c o n s t a n t i n d e p e n d e n t of r (1.4b)
T h e e q u a t i o n s which we have g i v e n d e f i n e the c l a s s i c s t e l l a r a t m o s p h e r e

p r o b l e m . Suppose t h a t the following a r e s p e c i f i e d : (i) t h e c h e m i c a l c o m p o -
sition of t h e a t m o s p h e r e ; (ii) t h e g r a v i t y , g; (iii) the flux c o n s t a n t F . We
c a n then solve the e q u a t i o n s (1. 1), (1.2) and ( 1 . 3 b ) , s u b j e c t to the b o u n d a r y
c o n d i t i o n s and t h e c o n s t r a i n t ( 1 . 4 b ) , to d e t e r m i n e all p r o p e r t i e s of the
a t m o s p h e r e , and to c o m p u t e t h e s p e c t r u m of the e m e r g e n t r a d i a t i o n .
T h e s o l u t i o n s a r e s u c h t h a t p, p and T d e c r e a s e o u t w a r d s . High in
t h e a t m o s p h e r e , p and p d e c r e a s e e x p o n e n t i a l l y with height and T t e n d s
to a c o n s t a n t v a l u e T fl (the " s u r f a c e t e m p e r a t u r e " ) . T h e o u t w a r d d e c r e a s e
of T i s e s s e n t i a l to an u n d e r s t a n d i n g of the o b s e r v e d s p e c t r u m . It i s , of
c o u r s e , o b v i o u s t h a t the h i g h e s t l a y e r s m u s t be the c o l d e s t , s i n c e t h e s e
l a y e r s c a n r a d i a t e f r e e l y to o u t e r s p a c e .
C o n s i d e r a p h o t o n , c r e a t e d at a p o i n t r , which m o v e s in t h e o u t w a r d
d i r e c t i o n r . T h e p r o b a b i l i t y t h a t t h i s photon e s c a p e s , without being r e -
absorbed, is ехр(-ти ) where
(1.5)
Г
T h e o b s e r v e d a t m o s p h e r e , at f r e q u e n c y v, e x t e n d s down to a depth r such

t h a t Ту (r) = 1. C o n s i d e r s o m e s u i t a b l e m e a n v a l u e , т , of tv . If т(г) = 1
and r ( r + A r ) i s s m a l l , s a y т ( г + A r ) - 0.01, t h e n A r i s the t h i c k n e s s of
the a t m o s p h e r e .
L e t u s c o n s i d e r how, in p r a c t i c e , our e q u a t i o n s m i g h t be s o l v e d . We
s t a r t with s o m e e s t i m a t e of T ( r ) and of Iv (r, 6). T h e n , using E q s (1.1)
and (1.2), we c a n c a l c u l a t e p ( r ) and p ( r ) and, a s s u m i n g a l l of the n e c e s s a r y
a t o m i c p h y s i c s to be known, we c a n c a l c u l a t e the a b s o r p t i o n c o e f f i c i e n t
к у ( r ) and the e m i s s i v i t y j v ( r ) . We c a n then s o l v e the t r a n s f e r e q u a t i o n (1.3b),
s u b j e c t to t h e b o u n d a r y c o n d i t i o n s but — u n l e s s we had b e e n given the c o r r e c t
solution to s t a r t with— the condition (1.4b) w i l l not be s a t i s f i e d . We m u s t
t h e r e f o r e a d j u s t T ( r ) until t h i s c o n d i t i o n i s s a t i s f i e d . We t h u s obtain new
e s t i m a t e s of T ( r ) and I (r, 0) and the p r o c e s s c a n be r e p e a t e d and, one
hopes, will be c o n v e r g e n t . F i n a l l y , if one i s t r y i n g to m a t c h t h e o r y and
o b s e r v a t i o n s f o r a r e a l s t a r , one m u s t a d j u s t F , g and c h e m i c a l c o m p o s i t i o n
so a s to get a g r e e m e n t b e t w e e n t h e c o m p u t e d and t h e o b s e r v e d s p e c t r a .
T h e g e n e r a l p i c t u r e on a b u n d a n c e s i s t h a t h y d r o g e n i s by f a r the m o s t
abundant e l e m e n t . Next c o m e s He, with a b u n d a n c e 0.1 t i m e s t h a t of H,
by n u m b e r s of a t o m s . All o t h e r a t o m s have m u c h l o w e r a b u n d a n c e s — in
total about 10" t i m e s t h e H a b u n d a n c e . S p e c t r u m l i n e s of H and He a r e ,
h o w e v e r , p r o d u c e d e f f i c i e n t l y only at r a t h e r high t e m p e r a t u r e s . In m a n y
a s t r o n o m i c a l s p e c t r a m o s t of the o b s e r v e d l i n e s a r e p r o d u c e d by e l e m e n t s
o t h e r t h a n H and H e .
What a t o m i c p h y s i c s i s r e q u i r e d ? Given the t e m p e r a t u r e , p r e s s u r e
and r a d i a t i o n field one m u s t f i r s t , f o r e a c h e l e m e n t , c o m p u t e the n u m b e r
of a t o m s in e a c h i o n i z a t i o n s t a g e and t h e n , f o r e a c h s t a g e , the n u m b e r in
e a c h e x c i t e d s t a t e . Knowing a l l r a d i a t i v e t r a n s i t i o n p r o b a b i l i t i e s , KV and
j„ c a n now be c o m p u t e d . E v i d e n t l y t h i s i s a p r e t t y daunting t a s k .
L e t us c o n s i d e r a s i m p l e r a p p r o x i m a t i o n . V e r y f a r f r o m the s u r f a c e
(t » 1), c o n d i t i o n s m u s t be c l o s e to t h o s e .in a b l a c k body at the l o c a l
264 SEATON
temperature T(r). We then have local t h e r m o d y n a m i c e q u i l i b r i u m ( L T E ) .

F o r a b l a c k body, = B„(T) w h e r e
1 1 (i 6)
^ m ^ W s ) " } ' -
i s the P l a n c k i n t e n s i t y . F o r a black body we a l s o have dl^ / d i = 0 and
hence, f r o m ( 1 . 3 a )
(]„/*„) = B„(T) (1.7)
T h i s i s K i r c h h o f f ' s l a w . But now the r a t i o (j / к ) d e p e n d s only on the

s t a t e of t h e m a t e r i a l p a r t i c l e s . If t h i s s t a t e i s c o n s i s t e n t with t h e r m o d y n a m i c
l a w s (Maxwell law, B o l t z m a n n law and Saha law of i o n i z a t i o n e q u i l i b r i u m )
t h e n (1.7) w i l l be s a t i s f i e d . In t h e L T E t h e o r y of s t e l l a r a t m o s p h e r e s ,
the K i r c h h o f f law (1. 7) i s a s s u m e d , but t h e P l a n c k law, I „ ( r , 6) = B „ ( T ( r ) ) ,
i s not a s s u m e d . C l e a r l y one could not a s s u m e the P l a n c k law, c o n s i s t e n t
with t h e b o u n d a r y condition that, at t h e top of the a t m o s p h e r e , a l l r a d i a t i o n
i s in t h e o u t w a r d d i r e c t i o n . T h e LTE a s s u m p t i o n w i l l be v a l i d if c o l l i s i o n a l
p r o c e s s e s a r e m u c h m o r e i m p o r t a n t than r a d i a t i v e p r o c e s s e s in d e t e r m i n i n g
the i o n i z a t i o n e q u i l i b r i u m and the level p o p u l a t i o n s . In the L T E a p p r o x i m a t i o n ,
c o l l i s i o n c r o s s - s e c t i o n s a r e not r e q u i r e d , but we s t i l l n e e d to know all
radiative transition probabilities.
In o r d e r to a p p r e c i a t e s o m e of the e s s e n t i a l s of the p r o b l e m , let us
now c o n s i d e r an e v e n s i m p l e r m o d e l . As a l r e a d y m e n t i o n e d , the o b s e r v e d
s p e c t r u m d e p e n d s in an e s s e n t i a l way on the t e m p e r a t u r e g r a d i e n t . In the
s i m p l e s t m o d e l one c o n s i d e r s a r e g i o n which e m i t s a p u r e continuum
s p e c t r u m , with i n t e n s i t y and above it a c o o l e r r e g i o n (the " r e v e r s i n g
l a y e r " ) w h i c h m a y be c o n s i d e r e d to a b s o r b r a d i a t i o n in s p e c t r u m l i n e s ,
but not to e m i t r a d i a t i o n . The o b s e r v e d i n t e n s i t y i s t h e n
I , = 1= e x p ( - r j (1.8)
where
rv = JPKV dr (1.9)
lev.
layer
C o n s i d e r a s p e c t r u m l i n e , involving an u p p e r l e v e l u and a l o w e r
l e v e l ft. T h e e m i s s i o n c o e f f i c i e n t i s given by
pj„= h a
uí hy
o ( 1 Л 0 )
the f a c t o r (l/Лтг) i s i n c l u d e d b e c a u s e the e m i s s i o n i s counted p e r unit

solid angle; N u i s t h e n u m b e r of a t o m s p e r unit v o l u m e in l e v e l u; A u {
i s the spontaneous t r a n s i t i o n probability; i s the f r e q u e n c y at the line
c e n t r e (hv 0 = (E u - E { ) w h e r e Е ц , E { a r e the a t o m i c e n e r g y l e v e l s ) ; and
<p(v) i s a n o r m a l i z e d line p r o f i l e f a c t o r ,
<p(v) di/ = 1 (1.11)

I A E A - S M R - 1 2 / 4 4 , 46 , 4 8 265
The a b s o r p t i o n c o e f f i c i e n t i s obtained using E q . (1. 7) and the B o l t z m a n n
= i£u exp (-hy 0 /kT) (1.12)
(u u , u e being s t a t i s t i c a l weights).
We obtain
2
pKv = — N, f i l - exp(-hi/ 0 /kT)} <p(v) (1.13)
where
f = A 1 4
8тг2 е 2 1/2 I T U £ ( ! • >
1
0
i s the a b s o r p t i o n o s c i l l a t o r s t r e n g t h . The f a c t o r {1 - exp(-hy Q /kT)} i s
a c o r r e c t i o n for s t i m u l a t e d e m i s s i o n : c o n s i s t e n t with the neglect of
spontaneous e m i s s i o n f o r the r e l a t i v e l y cold r e v e r s i n g l a y e r , we m a y
put t h i s f a c t o r equal to unity. We then have
2
(1Л5)
where
Л =/ N J dr (1.16)
rev.
layer
i s the n u m b e r of a t o m s in a column of unit a r e a , in the r e v e r s i n g l a y e r .
A s p e c t r u m line has a p r o f i l e a s shown in F i g . 1.
»V
FIG. 1. L i n e p r o f i l e ( i n t e n s i t y versus f r e q u e n c y ) .
The amount of a b s o r p t i o n in the line i s
f a l - i j d v (1.17)
The equivalent width of the line i s defined a s
Ay = / a s y ^ d v (1Д8)
266 SEATON
T h i s i s a u s e f u l q u a n t i t y , s i n c e no a b s o l u t e i n t e n s i t y c a l i b r a t i o n i s r e q u i r e d
and — so long a s t h e l i n e c a n b e c l e a r l y s e e n — the m e a s u r e d e q u i v a l e n t w i d t h
i s i n s e n s i t i v e to f r e q u e n c y r e s o l v i n g p o w e r .
F r o m E q . (1.9)
A v = / (1 - ехр(-т„ )) dy (1.. 19)
S u p p o s e t h a t t h e l i n e i s w e a k , so t h a t r v « 1 f o r a l l p o i n t s in t h e l i n e .
P u t t i n g (1 - expf-Tj, )) = т и and using (1.11) w e o b t a i n
2
f
Ли = Л Í1-20)
mť i
F o r s t r o n g e r l i n e s w e have to c o n s i d e r the f o r m of t h e p r o f i l e f a c t o r <p(v).

F o r p u r e t h e r m a l D o p p l e r b r o a d e n i n g w e h a v e <pv = cp® w h e r e
Л - i r f h - е х р { - Ы * - vü)/v,}2} (1.21)
and w h e r e
a = [Mc2/(2kT)]1/2 (1.22)
M being the atom m a s s . T h e f u l l w i d t h of t h e a b s o r p t i o n c o e f f i c i e n t , a t

half-maximum, is
= lü> [in(2)]1/2 (1.23)
(i.e.
S u p p o s e t h a t rv i s l a r g e at the l i n e c e n t r e , т„о » 1. F o r | v - v0 | > i Д°,
soon b e c o m e s s m a l l . All absorption is t h e r e f o r e effectively confined
to t h e r e g i o n (vQ - т Д ° ) S v S (v + | Д ° ) a n d w e h a v e
Ap^KAd (1.24)
w h e r e К i s a c o n s t a n t of o r d e r u n i t y .
F i n a l l y , f o r v e r y s t r o n g l i n e s , we h a v e to c o n s i d e r the a d d i t i o n a l
a b s o r p t i o n w h i c h o c c u r s f a r f r o m t h e l i n e c e n t r e . In t h i s r e g i o n t h e p r o f i l e
f a c t o r <p(v) i s d e t e r m i n e d by the f a c t t h a t a r a d i a t i n g a t o m s t a y s i n t h e
upper level for a finite time, t . This gives a profile
<p„2 = ^ {(v- y 0 ) 2 +Ó 2 }" 1 (1.25)
w h e r e 6 = l / ( 2 j r t u ) . W h e n t h e l o w e r l e v e l i s a l s o a n e x c i t e d s t a t e of f i n i t e
l i f e t i m e t h i s b e c o m e s б = (1/2тг) (t^ 1 + t j 1 ) . In g e n e r a l t h e l i f e t i m e s t , t t
a r e d e t e r m i n e d b o t h by r a d i a t i v e t r a n s i t i o n p r o b a b i l i t i e s and by c o l l i s i o n s .
T h e f o r m (1.25) i s r e f e r r e d to a s a d a m p i n g p r o f i l e o r L o r e n t z p r o f i l e .
C o m p a r e d w i t h (1.21) we s e e t h a t (1.25) d e c r e a s e s m u c h m o r e s l o w l y f o r
(v - y 0 ) l a r g e . T h e D o p p l e r p r o f i l e (1.21) u s u a l l y a p p l i e s n e a r t h e l i n e
c e n t r e ( (v - i/0) s m a l l ) , a n d t h e d a m p i n g p r o f i l e (1.25) a p p l i e s in t h e line
I A E A - S M R - 1 2 / 4 4 , 4 6 , 48 267
w i n g s . F o r v e r y s t r o n g l i n e s a b s o r p t i o n in the d a m p i n g wings i s i m p o r t a n t
and one o b t a i n s i n c r e a s e d e q u i v a l e n t w i d t h s , such t h a t
1/2
Av x (jrs f) (1.26)
C o m b i n i n g all t h e s e r e s u l t s , we m a y plot the e q u i v a l e n t width a s a

f u n c t i o n of J f t i ( n u m b e r of a b s o r b i n g a t o m s t i m e s o s c i l l a t o r s t r e n g t h ) .
Using l o g a r i t h m i c s c a l e s we o b t a i n F i g . 2. T h i s i s known a s the c u r v e
of g r o w t h .
log(ův)fconst
FIG.2. C u r v e of growth ( e q u i v a l e n t w i d t h versus n u m b e r of a b s o r b i n g a t o m s x o s c i l l a t o r s t r e n g t h ) .
We have 3 r e g i o n s : in r e g i o n A we have w e a k l i n e s and t h e l i n e a r r e l a t i o n

(1.20) holds; in r e g i o n В we have m e d i u m - s t r o n g l i n e s and the e q u i v a l e n t
width i s d e t e r m i n e d by the width of the D o p p l e r p r o f i l e , E q . (1.24); f i n a l l y
in r e g i o n С we have v e r y s t r o n g l i n e s , f o r which t h e r e i s a p p r e c i a b l e
a b s o r p t i o n in t h e d a m p i n g w i n g s , given by (1.26).
A m o r e r e f i n e d t h e o r y g i v e s a c u r v e of g r o w t h s i m i l a r to t h a t obtained
using o u r v e r y s i m p l e m o d e l of an a t m o s p h e r e containing two r e g i o n s . L e t
us c o n s i d e r t h e c a s e of the s o l a r s p e c t r u m . If we plot the o b s e r v e d
e q u i v a l e n t w i d t h s a g a i n s t ^f e f (as c o m p u t e d f r o m a model) we do i n d e e d
obtain a c u r v e of g r o w t h s i m i l a r to that shown in F i g . 1 — but with, of c o u r s e ,
a c e r t a i n a m o u n t of s c a t t e r .
We m a y now d i s c u s s in m o r e d e t a i l the a t o m i c d a t a needed f o r the
i n t e r p r e t a t i o n of the o b s e r v a t i o n s . F i r s t , the a s t r o p h y s i c i s t n e e d s to
know the o s c i l l a t o r s t r e n g t h s f. In r e c e n t y e a r s a g r e a t deal of w o r k h a s
b e e n done. A c c u r a t e a b s o l u t e m e a s u r e m e n t s have b e e n m a d e f o r s e l e c t e d
l i n e s , and f o r l i g h t e r a t o m s good a b s o l u t e r e s u l t s can be obtained f r o m
q u a n t u m m e c h a n i c a l c a l c u l a t i o n s . L a r g e n u m b e r s of r e l a t i v e f - v a l u e s c a n
be obtained f r o m o b s e r v e d l i n e i n t e n s i t i e s using l a b o r a t o r y light s o u r c e s
f o r which L T E can be a s s u m e d ; the data have to be c a l i b r a t e d a g a i n s t
a b s o l u t e m e a s u r e m e n t s . B u t d e s p i t e all t h e e f f o r t which p h y s i c i s t s have
put into t h e d e t e r m i n a t i o n of f - v a l u e s , the a s t r o p h y s i c i s t s a r e a l w a y s h u n g r y
f o r m o r e good new d a t a .
If one i s c o n c e r n e d with a b u n d a n c e a n a l y s i s f o r the sun, o r f o r b r i g h t
s t a r s , one m a y r e s t r i c t a t t e n t i o n to weak l i n e s on the l i n e a r p o r t i o n A of
the c u r v e of g r o w t h . F o r f a i n t e r s t a r s , h o w e v e r , one m u s t w o r k with
s t r o n g l i n e s , on the d a m p i n g p o r t i o n С of the c u r v e of g r o w t h . In m a n y
268 SEATON
c a s e s d a m p i n g i s due to c o l l i s i o n s with H a t o m s . No e x p e r i m e n t a l data

are available. Crude theoretical e s t i m a t e s can be made assuming van der
W a a l s f o r c e s . E x p e r i m e n t a l data a r e a v a i l a b l e f o r damping by c o l l i s i o n s
with r a r e g a s a t o m s . T h i s p r o v i d e s a c h e c k on the t h e o r y , and shows t h a t
the a s s u m p t i o n of van d e r W a a l s f o r c e s can give r e s u l t s in e r r o r by a
f a c t o r of 3 o r s o . A c c u r a t e c a l c u l a t i o n s have b e e n m a d e f o r a few s i m p l e
c a s e s — such a s d a m p i n g of Na l i n e s by H - a t o m c o l l i s i o n s — but no a c c u r a t e
data a r e a t p r e s e n t a v a i l a b l e f o r the g r e a t m a j o r i t y of l i n e s of i n t e r e s t to t h e
astrophysicist.
So f a r we have c o n c e n t r a t e d attention on the s p e c t r u m l i n e s . Let us
now t u r n to a d i f f e r e n t t o p i c , t h e continuous a b s o r p t i o n kv . T h i s m u s t be
known in o r d e r to c o n s t r u c t a model of a s t e l l a r a t m o s p h e r e . In t h e sun,
and in s t a r s not too d i f f e r e n t f r o m the sun, the c o n t i n u o u s a b s o r p t i o n in
the v i s i b l e i s due to H ,
H" + hv Ï* H + e (1.27)
Good a b s o l u t e c r o s s - s e c t i o n s a r e known both f r o m t h e o r y and f r o m l a b o r a t o r y

m e a s u r e m e n t s . In the i n f r a - r e d the f r e e - f r e e p r o c e s s
H + e + hi/s*H + e (1.28)
i s d o m i n a n t (the p r o c e s s H + e - ^ H + e + hy c a n be u n d e r s t o o d a s r a d i a t i o n
by an e l e c t r o n a c c e l e r a t e d by the field of an H a t o m ) . Good t h e o r e t i c a l
data a r e a v a i l a b l e .
M o s t of the H i s n e u t r a l and the e l e c t r o n s involved in (1.27) and (1.28)
c o m e f r o m i o n i z a t i o n of m e t a l a t o m s , having low i o n i z a t i o n p o t e n t i a l s . .
All the r a d i a t i v e and c o l l i s i o n a l p r o c e s s e s d e t e r m i n i n g the a m o u n t of H~
p r e s e n t have b e e n studied c a r e f u l l y , and it h a s b e e n shown that, f o r the
sun, the a s s u m p t i o n of L T E f o r the c a l c u l a t i o n of the c o n t i n u o u s a b s o r p t i o n
c o e f f i c i e n t i s a v e r y good a p p r o x i m a t i o n .
L e t us now t u r n to the h o t t e r s t a r s . F o r t h e s e , m o r e of the h y d r o g e n
i s i n e x c i t e d s t a t e s . Also m o r e r a d i a t i o n i s in the u l t r a - v i o l e t r e g i o n f o r
which p h o t o - i o n i z a t i o n of g r o u n d - s t a t e H c a n o c c u r . The c o n t i n u o u s
a b s o r p t i o n i s t h e n m a i n l y due to p h o t o - i o n i z a t i o n of H, f r o m the ground
s t a t e and f r o m e x c i t e d s t a t e s . P h o t o - i o n i z a t i o n of o t h e r a t o m s m u s t a l s o
be t a k e n into a c c o u n t . A f u r t h e r p r o c e s s of i m p o r t a n c e i s t h e s c a t t e r i n g
of r a d i a t i o n by f r e e e l e c t r o n s ,
e + hv - e + hy' (1.29)
which can c h a n g e the d i r e c t i o n of the photon and m u s t t h e r e f o r e be allowed

f o r in solving the t r a n s f e r equation, T h e p r o c e s s (1.29) which i s known a s
T h o m s o n s c a t t e r i n g , g i v e s only a s m a l l change in the photon e n e r g y (due to
the D o p p l e r e f f e c t a r i s i n g f r o m the e l e c t r o n v e l o c i t y ) .
In the m o s t e l a b o r a t e c a l c u l a t i o n s f o r m o d e l s of hot s t a r s , the L T E
a s s u m p t i o n h a s not b e e n m a d e : t h e H l e v e l p o p u l a t i o n s a r e c o m p u t e d
allowing f o r all p r o c e s s e s thought to be of i m p o r t a n c e . The c o n t r i b u t i o n
of the s t r o n g e r l i n e s to the t o t a l a b s o r p t i o n h a s a l s o b e e n t a k e n into a c c o u n t
in computing the m o d e l s .
F o r h o t t e r s t a r s the p r o f i l e s of the H l i n e s a r e of g r e a t i n t e r e s t . Due
to Í - d e g e n e r a c y , H e n e r g y l e v e l s have a l i n e a r S t a r k e f f e c t . The b r o a d e n i n g
I A E A - S M R - 1 2 / 4 4 , 46 , 48 269
i s t h e r e f o r e due to a v e r a g e e l e c t r i c f i e l d s p r o d u c e d by n e i g h b o u r i n g c h a r g e d
p a r t i c l e s . A g r e a t d e a l of e f f o r t h a s gone into p e r f e c t i n g the t h e o r y , which
is quite e l a b o r a t e . T h e H line w i d t h s depend on the p r e s s u r e in the a t m o s -
p h e r e which, in t u r n , d e p e n d s on the g r a v i t a t i o n a l c o n s t a n t g. The H line
p r o f i l e s a r e t h e r e f o r e used to d e t e r m i n e g.
If the L T E a s s u m p t i o n i s m a d e f o r hot s t a r s , it i s found that one c a n n o t
obtain a g r e e m e n t with o b s e r v a t i o n s f o r both the e q u i v a l e n t w i d t h s and the
p r o f i l e s of h y d r o g e n l i n e s . F u r t h e r m o r e , the v a l u e s of g deduced f r o m
the p r o f i l e s a r e not in a g r e e m e n t with v a l u e s deduced by o t h e r m e a n s .
T h e n o n - L T E c a l c u l a t i o n s a r e found to give m u c h m o r e s a t i s f a c t o r y r e s u l t s .
F o r m o s t s t a r s p r a c t i c a l l y a l l of the s p e c t r u m l i n e s a p p e a r in a b s o r p t i o n
but f o r c e r t a i n hot s t a r s with extended a t m o s p h e r e s one a l s o o b s e r v e s m a n y
e m i s s i o n l i n e s . C l e a r l y the L T E a s s u m p t i o n i s not v a l i d in the l o w - d e n s i t y
o u t e r l a y e r s of t h e s e s t a r s . Some p a r t i c u l a r l y i n t e r e s t i n g p r o b l e m s a r e
p o s e d by t h e s p e c t r u m of N III, f o r which s o m e of the l i n e s a p p e a r in e m i s s i o n
and s o m e in a b s o r p t i o n . E v e n f o r the c a s e of hot s t a r s which do not have
l o w - d e n s i t y extended a t m o s p h e r e s , s o m e of the N III l i n e s a p p e a r in e m i s s i o n .
T h e s e o b s e r v a t i o n s c a n be explained s a t i s f a c t o r i l y when one t a k e s e x p l i c i t
a c c o u n t of all the d e t a i l e d a t o m i c p r o c e s s e s which p o p u l a t e and depopulate
t h e N z + e n e r g y l e v e l s . F o r n o n - L T E c a l c u l a t i o n s , one r e q u i r e s l a r g e
a m o u n t s of a t o m i c data on r e a c t i o n r a t e s f o r c o l l i s i o n a l p r o c e s s e s , I s e e
t h e p a p e r by M i h a l a s and H u m m e r ] .
2. THE SOLAR CORONA
T h e r e g i o n of the s o l a r a t m o s p h e r e which g i v e s m o s t of the o b s e r v e d

r a d i a t i o n i s r e f e r r e d to a s the p h o t o s p h e r e . In the t h e o r y d i s c u s s e d in
s e c t i o n 1 it h a s b e e n a s s u m e d that t h i s r e g i o n i s q u i e s c e n t , that i s to s a y
t h a t t h e r e a r e no m a s s m o t i o n s . Having c o n s t r u c t e d a m o d e l we c a n c h e c k
on the c o n s i s t e n c y of t h i s a s s u m p t i o n .
Suppose that a s m a l l p e r t u r b a t i o n a c t s on an e l e m e n t of m a t e r i a l at r ,
and d i s p l a c e s it to r + S r . A l m o s t i n s t a n t a n e o u s l y t h i s e l e m e n t will r e a c h
p r e s s u r e e q u i l i b r i u m with i t s s u r r o u n d i n g s , but a m u c h l o n g e r t i m e will
be r e q u i r e d to r e a c h t h e r m a l e q u i l i b r i u m . We m a y t h e r e f o r e a s s u m e an
a d i a b a t i c change ( i . e . no h e a t e x c h a n g e ) . T h e new t e m p e r a t u r e of the
d i s p l a c e d e l e m e n t i s then T ( r ) + Ó T | a w h e r e A s t a n d s f o r a d i a b a t i c :
6T ЭТ ЭТ Эр
L (ár) (ár) (2.1)
Эг Эр А Эг M
w h e r e (dp/dr)|M i s the p r e s s u r e gradient for the model, calculated using

the m e t h o d s d e s c r i b e d in s e c t i o n 1. T h e t e m p e r a t u r e of the m o d e l at
r + 6r is T(r) + 6TIM where
dT
« T L = («г) d r (2.2)
In (2.1) the p a r t i a l d e r i v a t i v e (Эр/ЭТ) А i s e v a l u a t e d using the a d i a b a t i c

e q u a t i o n T 5 , p 1 _ ï = c o n s t a n t , w h e r e 7 i s the u s u a l r a t i o of s p e c i f i c h e a t s .
270 SEATON
If the d i s p l a c e d e l e m e n t i s c o l d e r than i t s s u r r o u n d i n g s , it will be d e n s e r

and will f a l l back to i t s o r i g i n a l p o s i t i o n . In t h i s c a s e t h e a t m o s p h e r e i s
s t a b l e and c o n v e c t i v e m o t i o n s will not d e v e l o p .
T h e condition f o r s t a b i l i t y i s
6T|A<6T|M (2.3)
F o r a m o d e l of the s o l a r a t m o s p h e r e it i s found that (2.3) i s s a t i s f i e d

only in t h e u p p e r l a y e r s , т <, 1. Below т convective motions occur
and t h e a c t u a l t e m p e r a t u r e g r a d i e n t i s then c l o s e to ( Э Т / Э г ) | А .
In t h e u p p e r l a y e r s m a s s m o t i o n s tend to be d a m p e d but s t i l l o c c u r
and m u s t be t a k e n into a c c o u n t in c o n s i d e r i n g the D o p p l e r b r o a d e n i n g of
the s p e c t r a l l i n e s .
T h e e x i s t e n c e of a c o n v e c t i v e r e g i o n at g r e a t e r d e p t h s , т > 1, p r o f o u n d l y
m o d i f i e s the c o n d i t i o n s in the v e r y h i g h e s t l a y e r s of the a t m o s p h e r e . T h i s
m a y be s e e n a s f o l l o w s . Convection p r o d u c e s a c o u s t i c e n e r g y , and an
a c o u s t i c e n e r g y fl ux, F sounc j, in the p h o t o s p h e r e . T h i s flux i s s m a l l c o m p a r e d
with the r a d i a t i v e flux, and t h e r e f o r e d o e s not s e r i o u s l y p e r t u r b the m a i n
p h o t o s p h e r i c l a y e r s . But what h a p p e n s f o r the u p p e r m o s t l a y e r s ? We have
r
sou„d = i P "s Л - (2.4)
w h e r e u s i s the a m p l i t u d e of p a r t i c l e d i s p l a c e m e n t v e l o c i t y due to the sound

wave, and v s = (ykT/ц) 1 ^ 2 i s the v e l o c i t y of sound. F o r the m o d e l we have
t h a t T -*• T„и a s r i n c r e a s e s , and hence t h a t vs t e n d s to a c o n s t a n t . But the
d e n s i t y p d e c r e a s e s e x p o n e n t i a l l y and c o n s e r v a t i o n of a c o u s t i c e n e r g y
t h e r e f o r e r e q u i r e s t h a t u s i n c r e a s e s e x p o n e n t i a l l y . E v e n t u a l l y the point
i s r e a c h e d w h e r e u s a p p r o a c h e s vs . At t h i s point the sound wave b e c o m e s
a s h o c k w a v e , and t h i s h e a t s t h e g a s . Beyond t h i s point all the a s s u m p t i o n s
m a d e in c o n s t r u c t i n g o u r m o d e l c e a s e to be v a l i d . In p l a c e of a c o n s t a n t
s u r f a c e t e m p e r a t u r e T 0 we have a t e m p e r a t u r e i n c r e a s e in the o u t e r m o s t
layers.
T h e t h e o r y d e s c r i b e d above i s a g r o s s o v e r - s i m p l i f i c a t i o n , but the
m a i n c o n c l u s i o n i s c o r r e c t : the e x i s t e n c e of a c o n v e c t i v e r e g i o n at g r e a t e r
d e p t h s p r o v i d e s a s o u r c e of e n e r g y which h e a t s the h i g h e s t l a y e r s . How
hot c a n t h e s e l a y e r s b e c o m e ? T h e e s c a p e v e l o c i t y v e , f o r an a t o m of
m a s s M, i s given by \ M v 2 = G M M 0 / R 0 w h e r e M Q i s the m a s s of the sun,
its r a d i u s .
O i 2
An e x t r e m e u p p e r l i m i t f o r T i s obtained on putting 2"Mve = k T . T h i s
g i v e s T = 2 X 10 K. In f a c t the o u t e r m o s t l a y e r s of the s o l a r a t m o s p h e r e —
the s o l a r c o r o n a — have a t e m p e r a t u r e of about 2X 10 6 K. At t h i s t e m p e r a -
t u r e t h e r e i s a s t e a d y outflow of m a t e r i a l , s i n c e p a r t i c l e s in the t a i l of the
Maxwell d i s t r i b u t i o n c a n e s c a p e (the " s o l a r w i n d " ) .
T h e t o t a l r a d i a t i o n f r o m the c o r o n a i s about 10" 6 of the r a d i a t i o n f r o m
the p h o t o s p h e r e . T h e c o r o n a can be o b s e r v e d d u r i n g an e c l i p s e (when the
p h o t o s p h e r i c r a d i a t i o n i s o b s c u r e d by the moon), o r by using a c o r o n a g r a p h
( i . e . an " a r t i f i c i a l e c l i p s e " ) . It can a l s o be o b s e r v e d a t u l t r a - v i o l e t and
X - r a y w a v e l e n g t h s (but only above t h e e a r t h ' s a t m o s p h e r e ) and at r a d i o
wavelengths.
In the c o r o n a we a r e c o n c e r n e d with t e m p e r a t u r e s of about 2 X 10 6 К
and d e n s i t i e s of o r d e r 2 X 10 8 cm" 3 , o r l e s s asône g o e s f u r t h e r out. T h e
g a s i s c o m p l e t e l y i o n i z e d . M o s t of the f r e e e l e c t r o n s c o m e f r o m i o n i z a t i o n
I A E A - S M R - 1 2 / 4 4 , 46 , 48 271
of H and H e . W i t h a H e / H a b u n d a n c e r a t i o of 0.1, by n u m b e r s of a t o m s ,
the e l e c t r o n d e n s i t y i s N e = 1.2 N(H + ). C o n d i t i o n s in the c o r o n a a r e f a r
f r o m u n i f o r m . M a g n e t i c f i e l d s , a s s o c i a t e d w i t h s u n s p o t s , a r e of i m p o r t a n c e .
T h e h i g h e s t t e m p e r a t u r e s o c c u r a t t h e m a x i m u m in t h e 1 1 - y e a r s u n s p o t c y c l e ,
and a r e a s s o c i a t e d w i t h a c t i v e s u n s p o t r e g i o n s .
The f r e e e l e c t r o n s in the corona s c a t t e r photospheric radiation (Thomson
s c a t t e r i n g ) . Since t h e s c a t t e r i n g c r o s s - s e c t i o n , ae = (ire2/mc), is inde-
p e n d e n t of f r e q u e n c y , t h e c o n t i n u u m s p e c t r u m of the c o r o n a i s s i m i l a r to
t h a t of t h e p h o t o s p h e r e . T h e r e a r e , h o w e v e r , two i m p o r t a n t d i f f e r e n c e s :
(i) t h e c o r o n a l c o n t i n u u m i s p o l a r i z e d ( t h i s i s a f e a t u r e of T h o m s o n s c a t t e r i n g ) ;
(ii) t h e p h o t o s p h e r i c a b s o r p t i o n l i n e s do not a p p e a r in t h e c o r o n a l c o n t i n u u m —
the e l e c t r o n v e l o c i t i e s a r e so h i g h t h a t a l l d e t a i l in the s p e c t r u m i s s m e a r e d
out by D o p p l e r e f f e c t s .
In t h e s p e c t r u m of the c o r o n a a t o p t i c a l w a v e l e n g t h s o n e o b s e r v e s
s p e c t r u m l i n e s due to t r a n s i t i o n s b e t w e e n f i n e s t r u c t u r e l e v e l s i n h i g h l y
i o n i z e d a t o m s . E x a m p l e ^ a r e F e X, 3p 5 2 P 1 / i 2 2
P3/2 6375 A, F e XIV
3p 2 P 3 / 2 - 2 P 1 / 2 a t 5303 A and C a XV 2p 2 3 Р г - 3 P 0 at 5694 A . T h e i o n i -
z a t i o n p o t e n t i a l s f o r p r o d u c t i o n of t h e o b s e r v e d i o n s a r e i n t h e r a n g e 200
to 1000 e V . T h e t e m p e r a t u r e c a n b e d e d u c e d f r o m c a r e f u l m e a s u r e m e n t s
of t h e l i n e w i d t h s , a s s u m e d due t o t h e r m a l D o p p l e r b r o a d e n i n g . T h e i o n i -
z a t i o n e q u i l i b r i u m i s d e t e r m i n e d by e l e c t r o n i m p a c t i o n i z a t i o n
X + e ->• X + e + e (2.5)
and r a d i a t i v e r e c o m b i n a t i o n ,
X + m + 1 + e - (X™ )* + h v (2.6)
It s h o u l d be n o t e d t h a t r e c o m b i n a t i o n m a y t a k e p l a c e to any e x c i t e d
s t a t e of X ™ , d e n o t e d by (X + m )*. Since t h e r a t e s of (2.5) a n d (2.6) a r e both
p r o p o r t i o n a l t o the e l e c t r o n d e n s i t y N e , t h e i o n a b u n d a n c e r a t i o N ( X + m ) /
N(X ) i s i n d e p e n d e n t of N e b u t i s v e r y s e n s i t i v e to t e m p e r a t u r e . One
can compute the f r a c t i o n a l ionization
Rm = N(X+m)/£N(X+n) (2.7)
n
It i s f o u n d t h a t , f o r a g i v e n i o n i z a t i o n s t a g e m , R m a p p r o a c h e s unity only
f o r a r a t h e r s m a l l r a n g e of T , a n d t h a t R m i s v e r y s m a l l o u t s i d e of t h i s
r a n g e . If s t r o n g r a d i a t i o n f r o m a g i v e n i o n i s o b s e r v e d the t e m p e r a t u r e
c a n be d e d u c e d . E a r l i e r c a l c u l a t i o n s of R m ( T ) g a v e t e m p e r a t u r e s a good
deal l o w e r than those deduced f r o m line p r o f i l e s . This d i s c r e p a n c y was
r e s o l v e d by B u r g e s s , who s h o w e d t h a t the r e c o m b i n a t i o n p r o c e s s (2.6) c a n
proceed via doubly-excited auto-ionizing states,
X + e ü (X )-'--'- -» (X )"- + hv (2.8)
T h i s i n c r e a s e s the r e c o m b i n a t i o n r a t e by a f a c t o r of o r d e r 10 1 - 10 2 , a n d
b r i n g s the t e m p e r a t u r e s d e d u c e d f r o m the i o n i z a t i o n e q u i l i b r i u m i n t o a g r e e -
m e n t with t e m p e r a t u r e s f r o m line p r o f i l e s .
272 SEATON
T h e s p e c t r u m l i n e s in the v i s i b l e c a n n o t be due to e l e c t r i c dipole r a d i -

ation, s i n c e t h e r e i s no c h a n g e in the p a r i t y of the i o n . T h e y a r e due to
m a g n e t i c dipole r a d i a t i o n . T h e r a d i a t i v e t r a n s i t i o n p r o b a b i l i t i e s c a n be
c a l c u l a t e d without d i f f i c u l t y . E x c i t a t i o n c a n be due to a n u m b e r of d i f f e r e n t
mechanisms.
(i) E x c i t a t i o n by a b s o r p t i o n of photo s p h e r i c r a d i a t i o n ,
X1 +hi/^X2 (2.9)
(ii) D i r e c t e x c i t a t i o n by e l e c t r o n i m p a c t ,
x ; m + e - X™ + e (2.10)
(iii) E l e c t r o n i m p a c t e x c i t a t i o n of h i g h e r l e v e l s , followed by c a s c a d e
Xj + e -» X 3 + e
m
x; - x ™ + hv (2.11)
If t h e t r a n s i t i o n 1 3 i s allowed f o r e l e c t r i c dipole r a d i a t i o n , and 1 2

f o r b i d d e n , t h e c r o s s - s e c t i o n Q ( 1 -<• 3) m a y be a f a c t o r of 10 o r so l a r g e r
t h a n Q(1 - 2).
(iv) E l e c t r o n i m p a c t e x c i t a t i o n v i a a u t o - i o n i z i n g l e v e l s ,
X™ + e к ( X ' ! n : - : ; ) - - X;m + e (2.12)
(v) E x c i t a t i o n by p r o t o n i m p a c t ,
X ™ + H + ~ X ™ + H+ (2.13)
In g e n e r a l , a l l of t h e s e p r o c e s s e s c o n t r i b u t e s i g n i f i c a n t l y . High in
the c o r o n a , w h e r e N e i s s m a l l , p r o c e s s (i) i s d o m i n a n t , while at l o w e r
l e v e l s p r o c e s s e s (iii) and (iv) a r e g e n e r a l l y d o m i n a n t . A g r e a t d e a l of
a t o m i c data i s r e q u i r e d in o r d e r to m a k e good c a l c u l a t i o n s of t h e i o n i -
z a t i o n e q u i l i b r i u m and of e x c i t a t i o n r a t e c o e f f i c i e n t s , and it i s only in
r e c e n t y e a r s t h a t t e c h n i q u e s f o r the c o m p u t a t i o n of t h e s e data have b e e n
d e v e l o p e d . F o r the q u a n t i t a t i v e i n t e r p r e t a t i o n of c o r o n a l line i n t e n s i t i e s ,
a g r e a t d e a l m o r e w o r k r e m a i n s to be done.
R a d i a t i o n f r o m i n t e r m e d i a t e i o n i z a t i o n s t a g e s (say 5 t i m e s i o n i z e d ,
r a t h e r than 10 to 15 t i m e s ) i s g e n e r a l l y not o b s e r v e d in t h e o p t i c a l r e g i o n ;
f o r t h e s e s t a g e s e l e c t r i c dipole t r a n s i t i o n s give r a d i a t i o n in the u l t r a -
v i o l e t and t r a n s i t i o n s b e t w e e n f i n e s t r u c t u r e l e v e l s give r a d i a t i o n in the
i n f r a - r e d . B u t e v e n in t h e u l t r a - v i o l e t ( o b s e r v a t i o n s f r o m r o c k e t s and
s a t e l l i t e s ) r a d i a t i o n f r o m t h e s e i o n s i s found to be c o m p a r a t i v e l y w e a k .
Such o b s e r v a t i o n s have b e e n v e r y i m p o r t a n t f o r gaining i n f o r m a t i o n about
t h e t e m p e r a t u r e s t r u c t u r e of the s u n ' s a t m o s p h e r e . In the p h o t o s p h e r e ,
at T — 1, the t e m p e r a t u r e i s T = 6000 K. At the " t o p " of the p h o t o s p h e r e
the t e m p e r a t u r e r e a c h e s a m i n i m u m v a l u e c l o s e r to 5000 K. It then r i s e s
to v a l u e s in the r a n g e 1 0 ' to 10 ü К i n t h e r e g i o n known a s the c h r o m o s p h e r e ,
and finally, r i s e s v e r y s t e e p l y to 2 X 10® К in the c o r o n a . The t e m p e r a t u r e
in t h i s s t e e p t r a n s i t i o n r e g i o n i s m a i n l y d e t e r m i n e d by t h e r m a l conduction.
I A E A - S M R - 1 2 / 4 4 , 46 , 48 273
S o l a r c o r o n a l i n e s o b s e r v e d at u l t r a - v i o l e t and X - r a y w a v e l e n g t h s
(the XUV r e g i o n ) a r e e x c i t e d by e l e c t r o n i m p a c t . A t t e m p t s a r e being m a d e
to d e t e r m i n e t e m p e r a t u r e s and d e n s i t i e s f r o m o b s e r v e d l i n e - i n t e n s i t y r a t i o s .
T h e XUV o b s e r v a t i o n s have b e e n of p a r t i c u l a r i n t e r e s t f o r the study of
l o c a l i z e d " a c t i v e r e g i o n s " , w h e r e T m a y be a s high a s 107 К o r m o r e .
In t h e s e r e g i o n s one o b s e r v e s i o n s s u c h a s F e XXV, i . e . h e l i u m - l i k e
i r o n . One a l s o o b s e r v e s m a n y l i t h i u m - l i k e i o n s .
3. GASEOUS N E B U L A E
In t h e i r a s t r o n o m i c a l s i g n i f i c a n c e the d i f f u s e e m i s s i o n line n e b u l a e
and the p l a n e t a r y n e b u l a e a r e quite d i f f e r e n t t y p e s of o b j e c t s . T h e d i f f u s e
n e b u l a e a r e a s s o c i a t e d with r e g i o n s of g a s and dust having a t o t a l m a s s of
o r d e r 1 0 5 M e (M Q = t h e m a s s of the sun). They a r e r e g i o n s of s t a r f o r -
m a t i o n . A m o n g t h e s t a r s f o r m e d a r e the hot, m a s s i v e and l u m i n o u s О
and В s t a r s . T h e s e s t a r s have an a p p r e c i a b l e e n e r g y output with f r e q u e n c y
v > v-y, w h e r e hp-y i s the t h r e s h o l d e n e r g y f o r i o n i z a t i o n of H ( l s ) . In c o n s e -
q u e n c e the g a s in the n e i g h b o u r h o o d of t h e s e s t a r s b e c o m e s i o n i z e d , and
g i v e s the o b s e r v e d e m i s s i o n - l i n e s p e c t r u m .
A p l a n e t a r y n e b u l a i s p r o d u c e d when an old, highly evolved s t a r e j e c t s
an o u t e r e n v e l o p e , having a m a s s of about 0.1 M Q , and l e a v e s behind a hot
c e n t r a l s t e l l a r c o r e , which p r o d u c e s r a d i a t i o n c a p a b l e of ionizing the
ejected gas.
The p h y s i c a l p r o c e s s e s in t h e s e two t y p e s of n e b u l a a r e v e r y s i m i l a r .
The p r i m a r y p r o c e s s i s p h o t o - i o n i z a t i o n . M o s t of the f r e e e l e c t r o n s c o m e
f r o m i o n i z a t i o n of H ( l s ) :
H ( l s ) + hp - H + + e (p> vx) (3.1)
If the a m o u n t of g a s p r e s e n t i s s u f f i c i e n t to a b s o r b all of the ionizing

r a d i a t i o n , it c a n be shown t h a t t h e r e i s a r a t h e r s h a r p b o u n d a r y b e t w e e n
the ionized g a s , and the n e u t r a l g a s which o c c u r s f u r t h e r away f r o m the
hot s t a r . W i t h i n t h e i o n i z e d r e g i o n the a m o u n t of n e u t r a l g a s i s s m a l l
N(H°)/N(H + ) being of o r d e r 10" 3 to 10" 4 .
The p r i m a r y p h o t o - i o n i z a t i o n p r o c e s s i s e v e n t u a l l y followed by r a d i -
tive r e c o m b i n a t i o n , which can be to any e x c i t e d s t a t e ,
H + + e - H(ni ) + hp' (3.2)
The excited s t a t e s d e c a y r a d i a t i v e l y
H(nf> ) -» H ( n ' i ' ) + hf n n . (3.3)
giving r a d i a t i o n which can be o b s e r v e d . E v e n t u a l l y the a t o m r e a c h e s the

g r o u n d s t a t e . The c o n d i t i o n s of d e n s i t y and of i n t e n s i t y of r a d i a t i o n a r e
such t h a t m o s t n e u t r a l H i s in the g r o u n d s t a t e . In c o n s i d e r i n g the i o n i -
z a t i o n e q u i l i b r i u m , i o n i z a t i o n f r o m the g r o u n d s t a t e i s the only i o n i z a t i o n
p r o c e s s which n e e d be c o n s i d e r e d .
E l e c t r o n - e l e c t r o n c o l l i s i o n s a r e v e r y e f f e c t i v e in r e d i s t r i b u t i n g
e l e c t r o n k i n e t i c e n e r g y and it m a y t h e r e f o r e be a s s u m e d t h a t the e l e c t r o n s
have a Maxwell d i s t r i b u t i o n and an e l e c t r o n t e m p e r a t u r e , T . T h e e l e c t r o n
d e n s i t y i s denoted by N e .
274 SEATON
In the p r e s e n t s e c t i o n we t a k e r a d i a t i o n i n t e n s i t y I to be m e a s u r e d in
q u a n t a p e r unit a r e a , p e r unit t i m e , p e r unit solid angle (in s e c t i o n 1 we
took I to be in units of e n e r g y p e r unit a r e a , e t c . )
The i o n i z a t i o n e q u i l i b r i u m . With N(H°) = N(H(ls)), the n u m b e r of ioni-

z a t i o n s (3.1) p e r unit v o l u m e p e r unit t i m e i s
oo
N(H°) 4 т г J , dy (3.4)
"i
w h e r e a 1 (i/) i s the c r o s s - s e c t i o n f o r (3.1) and w h e r e J^ i s the i n t e n s i t y
averaged over direction,
3 5
= / ^ < - >
w h e r e du i s an e l e m e n t of solid a n g l e . The n u m b e r of r e c o m b i n a t i o n s to
l e v e l n i (Eq. (3.2)) i s a B l N(H + ) N e .
The equation f o r the i o n i z a t i o n e q u i l i b r i u m i s t h e r e f o r e
OO OO
N(H°)4tt f a 1 ( v ) J u d v = - N ( K + ) N e Y j % (3.6)
щ n=l
where an = . T h e i n t e n s i t y J„ h a s two c o m p o n e n t s : r a d i a t i o n f r o m
i
the c e n t r a l s t a r and r a d i a t i o n p r o d u c e d in the n e b u l a . T h e r e c o m b i n a t i o n
p r o c e s s (3.2) g i v e s a photon with e n e r g y
hi/' = hy n + I m v 2 (3.7)
w h e r e vn = ь^/п 2 i s t h e t h r e s h o l d f r e q u e n c y f o r i o n i z a t i o n f r o m l e v e l n,
and \ m v 2 i s the k i n e t i c e n e r g y of the i n c i d e n t e l e c t r o n . We s h a l l s e e
l a t e r t h a t T e = 1 0 4 K giving \ m v 2 = kT e - 1 eV which i s s m a l l c o m p a r e d
to hy x = 13.6 eV. It t h e r e f o r e f o l l o w s t h a t y' < v^ f o r n > 1; t h a t i s to
s a y , only g r o u n d - s t a t e r e c o m b i n a t i o n s p r o d u c e quanta which can be r e -
a b s o r b e d in the i o n i z a t i o n p r o c e s s (3.1). We m a y t h e r e f o r e w r i t e J^ f o r
У > У1 a s the s u m of two p a r t s :
j, = j r ° +JÍ4 (3.8)
w h e r e J^,star' i s r a d i a t i o n f r o m the s t a r and J^ 1 ' r a d i a t i o n f r o m g r o u n d -

state recombinations.
The H p h o t o - i o n i z a t i o n c r o s s - s e c t i o n s a n ^(y) can be computed e x a c t l y
and the r e c o m b i n a t i o n c o e f f i c i e n t s a n l (T e ) c a n be e x p r e s s e d in t e r m s of
t h e p h o t o - i o n i z a t i o n c r o s s - s e c t i o n s (the r e q u i r e d r e l a t i o n s w e r e given in
t h e a u t h o r ' s 1961 B o u l d e r p a p e r s — s e e r e f e r e n c e s to Introduction). The g r o u n d -
s t a t e p h o t o - i o n i z a t i o n c r o s s - s e c t i o n aj^ ( y) d e c r e a s e s r a t h e r r a p i d l y a s a f u n c t i o n
of v, r o u g h l y a s y" 3 . Q u a n t a f r o m g r o u n d - s t a t e r e c o m b i n a t i o n have hy'
c l o s e to h i ^ . At t h e s e f r e q u e n c i e s a x ( y ) i s c o m p a r a t i v e l y l a r g e . It i s
t h e r e f o r e o f t e n a good a p p r o x i m a t i o n to a s s u m e t h a t t h e s e q u a n t a a r e r e -
a b s o r b e d at a point c l o s e to t h a t at which they a r e p r o d u c e d . We t h e n have
I A E A - S M R - 1 2 / 4 4 , 4 6 , 48 275
N ( H C ) 4 t t f a ^ v ) J ^ d v = N(H + ) N e a^ (3.9)
Vl
and h e n c e , f r o m (3.6), (3.8) a n d (3.9),

co
N ( H ° ) 4 t t J a ^ v ) J ( „ star) dv = N(H + )N e o- B (3.10)
where
а„В =/L_ апJ
n =2
L e t t h e s t a r h a v e a l u m i n o s i t y Lv dv p h o t o n s p e r unit t i m e . If w e
n e g l e c t a b s o r p t i o n , t h e n u m b e r of p h o t o n s c r o s s i n g unit a r e a on a s p h e r e
a t a d i s t a n c e r f r o m t h e s t a r , i s L „ dv/(Airr2) p e r unit t i m e . T h i s i s t h e
s a m e q u a n t i t y a s 47rj£ s t a r ) d v ; i . e . in t h e a b s e n c e of a b s o r p t i o n
4,rJ< s t a r ) = ~LVI (47гг 2 ) (3.11)
T h e e f f e c t of a b s o r p t i o n i s to r e d u c e j ( s t a r ) by a f a c t o r е х р ( - т ^ ) w h e r e
r
r„ (r) = a - L ( i / ) f v H H ° ) d r < (3.12)
о
T h e f i n a l e x p r e s s i o n f o r the i o n i z a t i o n e q u i l i b r i u m i s t h e r e f o r e
J ^ a ^ (i/) L „ e x p { - T U (r ))d у = N e N(H + ) а в (3.13)

"i
It i s now s e e n how a n i o n i z a t i o n m o d e l c a n be c o m p u t e d . We i n t e g r a t e
o u t w a r d s . At e a c h p o i n t w e u s e (3.13) to c o m p u t e N(H° ), e x t r a p o l a t e to
t h e n e x t p o i n t , c a l c u l a t e t h e i n c r e m e n t in Tv (r) f r o m (3.12), a n d t h e n c o m p u t e
N(H°) a t t h i s n e x t p o i n t u s i n g (3.13). If n e c e s s a r y i t e r a t i o n s a r e r e p e a t e d
until the p r o c e s s c o n v e r g e s .
S u p p o s e t h a t a l l of t h e i o n i z i n g r a d i a t i o n i s a b s o r b e d . T h e n f r o m
i n t e g r a t i o n of (3.13) o v e r t h e e n t i r e v o l u m e — o r f r o m e q u a t i n g the t o t a l
n u m b e r of p h o t o n s to t h e t o t a l n u m b e r of i o n i z a t i o n s — w e o b t a i n
J L v d y = J N e N ( H )orB dV (3.14)
"i
T h e h y d r o g e n r e c o m b i n a t i o n s p e c t r u m . In t h e e a r l i e s t w o r k t h e q u a n t u m
n u m b e r i w a s not i n c l u d e d . It w a s i m p l i c i t l y a s s u m e d t h a t
(2
N(H(n*)) = * t 1 } Nn (3.15)
2 7 6 SEATON
w h e r e Nn i s t h e n u m b e r of a t o m s in l e v e l n (Eq. (3.15) i s t r u e in t h e r m o -
d y n a m i c e q u i l i b r i u m ) . A s s u m i n g l e v e l n to be p o p u l a t e d by r a d i a t i v e
c a p t u r e and by c a s c a d e f r o m h i g h e r l e v e l s , and d e p o p u l a t e d by s p o n t a n e o u s
e m i s s i o n , we have
«nNeN(H + ) + £ Nn.An.n = N n £ A nn .. (3.16)

n' > n n" < n
w h e r e the A ' s a r e E i n s t e i n s p o n t a n e o u s e m i s s i o n c o e f f i c i e n t s .
We m a y solve the e q u a t i o n s (3.16) and c o m p u t e the r a t e of e m i s s i o n
of q u a n t a p e r unit v o l u m e in a s p e c t r a l l i n e ,
= NnAnn. (3.17)
Since N n i s p r o p o r t i o n a l to N e N(H + ) we m a y put
4*j„„' = N e N ( H + ) a n n . (3.1«)
w h e r e a n n ' i s the e f f e c t i v e r e c o m b i n a t i o n c o e f f i c i e n t f o r p r o d u c t i o n of
the l i n e .
A f u r t h e r point to be c o n s i d e r e d i s w h e t h e r r e - a b s o r p t i o n of line
r a d i a t i o n i s i m p o r t a n t . It t u r n s out that r e - a b s o r p t i o n f r o m e x c i t e d s t a t e s
i s g e n e r a l l y not i m p o r t a n t but t h a t r e - a b s o r p t i o n f r o m the g r o u n d s t a t e
can be v e r y i m p o r t a n t . C o n s i d e r the c a s e of a Ly-ß photon ( t r a n s i t i o n
n = 3 to n' = 1). R e - a b s o r p t i o n ,
H(n = 1) + hv 3 1 - H(n = 3) (3.19)
c a n be followed by r e - e m i s s i o n of Ly ß o r by c o n v e r s i o n to two p h o t o n s ,
hv 3 2 and hi/ 21 :
H(n = 3) -* H(n = 2) + hy 32 (3>20)
H(n = 2) - H(n = 1) + hv 21
If the a b s o r p t i o n p r o c e s s (3.19) t a k e s p l a c e m a n y t i m e s , t h e n it i s e v e n t u a l l y
followed by (3.20). T h e net e f f e c t i s t h e s a m e a s a s s u m i n g that the t r a n s i t i o n
3 -* 1 d o e s not o c c u r a t a l l . It i s found t h a t , f o r n e a r l y a l l n e b u l a e , t h e s a m e
a r g u m e n t a p p l i e s to a l l n 1 t r a n s i t i o n s . We c a n t a k e t h e s e p r o c e s s e s into
a c c o u n t by s i m p l y o m i t t i n g the c o n t r i b u t i o n f r o m n" = 1 in (3.16).
In t h e v i s i b l e r e g i o n one o b s e r v e s the B a l m e r l i n e s , n n' with n1 = 2;
and in the n e a r i n f r a - r e d the P a s c h e n l i n e s , n n ' with n1 = 3. T h e r e l a t i v e
i n t e n s i t i e s a r e i n d e p e n d e n t of d e n s i t y . In p r i n c i p l e they depend on T e but
in p r a c t i c e a r e found to be i n s e n s i t i v e to T g .
T h e o b s e r v e d r e l a t i v e i n t e n s i t i e s a g r e e r e a s o n a b l y w e l l with t h o s e
c a l c u l a t e d u s i n g the e l e m e n t a r y t h e o r y which we have d e s c r i b e d , so long
a s a l l o w a n c e i s m a d e f o r a b s o r p t i o n by i n t e r s t e l l a r dust:
X 1 0 C f ( M
Observed W = Emitted W " <3-21>
w h e r e с i s a m e a s u r e of the a m o u n t of a b s o r b i n g m a t e r i a l along the line

of s i g h t and f(X) g i v e s t h e w a v e l e n g t h d e p e n d e n c e of t h e a b s o r p t i o n . Many
I A E A - S M R - 1 2 / 4 4 , 46 , 48 277
a s t r o n o m i c a l o b s e r v a t i o n s i n d i c a t e t h a t — to a good a p p r o x i m a t i o n — f(X)
i s a l w a y s the s a m e ( i . e . the o p t i c a l p r o p e r t i e s of the a b s o r b i n g m a t e r i a l
a r e e v e r y w h e r e the s a m e ) . In c o m p a r i n g o b s e r v e d and c a l c u l a t e d r e l a t i v e
i n t e n s i t i e s we t h e r e f o r e have one a d j u s t a b l e p a r a m e t e r , с in e q u a t i o n (3.21).
M o r e r e f i n e d t h e o r y of the h y d r o g e n r e c o m b i n a t i o n s p e c t r u m . All of the

e a r l i e r o b s e r v a t i o n a l w o r k w a s done using p h o t o g r a p h i c p h o t o m e t r y . F o r
r e l a t i v e H line i n t e n s i t i e s t h e r e w a s good a g r e e m e n t b e t w e e n o b s e r v a t i o n s
and t h e o r y f o r the s t r o n g e r l i n e s , but s o m e s e r i o u s d i s c r e p a n c i e s f o r the
f a i n t e r high B a l m e r l i n e s . T h i s d i s c r e p a n c y w a s l a r g e l y r e s p o n s i b l e f o r
s t i m u l a t i n g m u c h m o r e t h o r o u g h i n v e s t i g a t i o n s of the t h e o r y of the H r e c o m -
b i n a t i o n s p e c t r u m . In the p a s t few y e a r s new m e a s u r e m e n t s have b e e n
m a d e using m o d e r n p h o t o - e l e c t r i c s c a n n e r t e c h n i q u e s , and it h a s b e e n
shown t h a t t h e e a r l i e r d i s c r e p a n c i e s with t h e o r y w e r e due to c a l i b r a t i o n
e r r o r s in p h o t o g r a p h i c p h o t o m e t r y of f a i n t l i n e s . It t u r n s out, h o w e v e r ,
t h a t t h e r e f i n e m e n t s in the t h e o r y a r e v e r y i m p o r t a n t f o r the i n t e r p r e t a t i o n
of l i n e s o b s e r v e d at r a d i o w a v e l e n g t h s ; we s h a l l r e t u r n to t h i s s u b j e c t
l a t e r on.
F i r s t we m u s t c o n s i d e r the n í s t a t e s . C o l l i s i o n a l r e d i s t r i b u t i o n in i
by p r o t o n i m p a c t
H(n, SL ) + H H(n, í ± 1) + H" (3.22)
h a s v e r y l a r g e r a t e c o e f f i c i e n t s , but at t y p i c a l d e n s i t i e s in n e b u l a e
(Ne = 10 4 cm" 3 o r l e s s ) (3.22) i s not an i m p o r t a n t p r o c e s s f o r n l e s s t h a n
about 20. Below t h i s l e v e l the p o p u l a t i o n s of t h e ní s t a t e s m u s t be c a l c u -
l a t e d allowing f o r all r a d i a t i v e c a p t u r e and c a s c a d e p r o c e s s e s .
F o r l a r g e r v a l u e s of n, s a y n > 40, (3.22) i s v e r y e f f e c t i v e and e q u a t i o n
(3.15) m a y be a s s u m e d . B u t f o r t h e s e highly e x c i t e d s t a t e s o t h e r c o l l i s i o n a l
processes,
H(n) + e ** H(n') + e (3.23)

+
H(n) + e ** H + e + e (3.24)
m u s t b e c o n s i d e r e d . T h e p h y s i c s of such p r o c e s s e s a r e d i s c u s s e d in t h e
p a p e r s by P e r c i v a l .
T h e p r e s e n t p o s i t i o n s e e m s to b e v e r y s a t i s f a c t o r y : the m o s t c a r e f u l
p h o t o - e l e c t r i c s c a n n e r o b s e r v a t i o n s , and t h e b e s t c a l c u l a t i o n s taking into
a c c o u n t a l l r e l e v a n t r a d i a t i v e and c o l l i s i o n a l p r o c e s s e s , a r e in a g r e e m e n t
to within the a c c u r a c y of f u n d a m e n t a l s p e c t r o p h o t o m e t r i c c a l i b r a t i o n s .
The He r e c o m b i n a t i o n s p e c t r a . In n e b u l a e with the h o t t e s t c e n t r a l stars

s o m e of the h e l i u m i s doubly i o n i z e d and one o b s e r v e s t h e He II s p e c t r u m
( e m i t t e d by He + following r e c o m b i n a t i o n of H e 2 + ) . The t h e o r y i s s i m i l a r
to t h a t f o r H.
In m a n y n e b u l a e one a l s o o b s e r v e s the He I r e c o m b i n a t i o n s p e c t r u m .
T h e t h e o r y d i f f e r s f r o m t h a t f o r H i n t h r e e r e s p e c t s , (i) R a d i a t i v e t r a n s i t i o n
p r o b a b i l i t i e s f o r He a r e not known e x a c t l y , a s they a r e f o r H, but m a y be
c a l c u l a t e d to high a c c u r a c y , (ii) T h e ní s t a t e s in He a r e not d e g e n e r a t e
with r e s p e c t to SL. (iii) The He l e v e l s 2 1 S and 2 3 S a r e m e t a s t a b l e .
278 SEATON
He 2 1 S can decay by t w o - p h o t o n e m i s s i o n
He(2 1 S) H e ( l x S ) + hp + h i / (3.25)
and by c o l l i s i o n a l t r a n s i t i o n s to 2 1 P followed by o n e - p h o t o n t r a n s i t i o n s
to 1 S. T h e p r o b a b i l i t i e s f o r t h e s e p r o c e s s e s a r e s u f f i c i e n t l y l a r g e that
the m e t a s t a b i l i t y of 2 "'"S need not n o r m a l l y be t a k e n into a c c o u n t .
Two-photon e m i s s i o n by 2 3 S h a s a v e r y s m a l l p r o b a b i l i t y . A m u c h
m o r e i m p o r t a n t p r o c e s s i s the o n e - p h o t o n m a g n e t i c dipole t r a n s i t i o n
He(2 3 S) -* H e ( l 1 S) + hy (3.26)
which i s allowed when r e l a t i v i s t i c e f f e c t s a r e t a k e n into a c c o u n t . He 2 3 S

can a l s o be d e p o p u l a t e d by c o l l i s i o n a l t r a n s i t i o n s to 2 1 S and 2 1 P . In m a n y
c a s e s t h e p o p u l a t i o n of 2 3 S r e m a i n s l a r g e and one m u s t allow f o r r e -
a b s o r p t i o n of line r a d i a t i o n f r o m 2 3S and f o r c o l l i s i o n a l ( e l e c t r o n i m p a c t )
e x c i t a t i o n f r o m 2 3 S.
When all of t h e s e p r o c e s s e s a r e t a k e n into a c c o u n t t h e c o m p u t e d r e l a t i v e
He I i n t e n s i t i e s a r e in good a g r e e m e n t with o b s e r v a t i o n s . P r o m the He to H
i n t e n s i t y r a t i o s one m a y d e d u c e the a b u n d a n c e r a t i o N(He)/N(H). F o r m a n y
d i f f e r e n t o b j e c t s it i s found that N(He)/N(H) = 0.10 ± 0.02. T h i s r e s u l t h a s
p r o f o u n d c o s m o l o g i c a l s i g n i f i c a n c e ; f r o m t h e r e s u l t s of c a r e f u l , and o f t e n
d i f f i c u l t , o b s e r v a t i o n s , and f r o m a d e t a i l e d study of a wide r a n g e of a t o m i c
p r o c e s s e s one o b t a i n s a r e s u l t which h a s i m p o r t a n t i m p l i c a t i o n s c o n c e r n i n g
the n a t u r e of t h e U n i v e r s e .
The f o r b i d d e n line s p e c t r u m . Many of the s t r o n g e s t l i n e s i n t h e s p e c t r a

of n e b u l a e a r e due to f o r b i d d e n t r a n s i t i o n s in c o m m o n ions, such a s N + , 0 + ,
0 2 + , . . . . We d i s c u s s two c a s e s , 0 2 + and 0 + .
T h e t h r e e l o w e s t e n e r g y l e v e l s in 0 2 + a r e 2s 2 2p 2 3 P , 1 D, 1 S. The
s t r o n g e s t l i n e s in m a n y n e b u l a r s p e c t r a a r e due to the t r a n s i t i o n 0 2 + 1 D -» 3 P .
T h e l i n e due to 1 S -* i s a l s o o b s e r v e d but i s m u c h f a i n t e r . T h e upper
l e v e l s a r e e x c i t e d by e l e c t r o n i m p a c t
02+ (3P) + e - 02+ ( Ъ ) + e (3.27)

2+ 3 2+
0 ( P) + e - 0 ^S) + e (3.28)
Denote t h e t h r e e l e v e l s , 3 P , a D and 1 S, by s u b s c r i p t s 1, 2 and 3,

r e s p e c t i v e l y . L e t q 1 2 a n d q 1 3 be the r a t e c o e f f i c i e n t s f o r (3.27) and (3.28).
T h e c o e f f i c i e n t s f o r the i n v e r s e p r o c e s s e s a r e
=
421 2"qi2 ex
P(E2l/kT> < 3 - 29 >
q 3 1 = H i q i 3 exp(E 3 1 / k T ) (3.30)
w h e r e the a r e s t a t i s t i c a l w e i g h t s and Ejj = (Ei - E j ) . T h e d e - e x c i t a t i o n

c o e f f i c i e n t s q ^ v a r y slowly with Te but the e x c i t a t i o n c o e f f i c i e n t s q-^ have
an e x p o n e n t i a i d e p e n d e n c e , е х р ( - Е д / к Т е ) . F o r N e « 1 0 4 cm" 3 s p o n t a n e o u s
r a d i a t i v e t r a n s i t i o n s f r o m -"-D and Щ a r e m u c h m o r e p r o b a b l e t h a n c o l -
l i s i o n a l d e - e x c i t a t i o n . The e m i s s i o n p e r unit v o l u m e f o r t h e 2 1 and
3 - 2 t r a n s i t i o n s i s then
IAEA-SMR-12/44, 46 , 48 279
4*32! = N e N i q i 2 = N e N i - A q 2 1 e x p ( - E 2 1 / k T e ) (3.31)
u».
and
4^32 = NeN!q13
(3.32)
N e N ^ q ^ /кТ£)
l
It should be noted t h a t t h e e m i s s i o n r a t e e q u a l s t h e e x c i t a t i o n r a t e . In (3.31)

we n e g l e c t a s m a l l c o r r e c t i o n f o r c a s c a d e f r o m l e v e l 3. In (3.32) we h a v e
to i n c l u d e a b r a n c h i n g - r a t i o f a c t o r , A 3 2 / ( A 3 2 + A 3 1 ) . T h e r a t i o of l i n e
i n t e n s i t i e s ( i . e . r a t i o s of n u m b e r s of q u a n t a ) i s
(3.33)
(recalling that E 3 2 = E31 - E 2 1 ) .

T h i s i s s m a l l b e c a u s e ( E 3 2 / k T £ ) i s s m a l l . M e a s u r e m e n t of t h e r a t i o
I 3 2 / I 2 1 p r o v i d e s a v e r y c o n v e n i e n t m e a n s of d e t e r m i n i n g T £ . O n c e t h i s i s
known, t h e r a t i o of t h e 0 2 + l i n e i n t e n s i t i e s to H l i n e i n t e n s i t i e s g i v e s t h e
r a t i o ( n u m b e r of 0 2 + i o n s ) / ( n u m b e r of H + i o n s ) .
T h e 0 + ion h a s l e v e l s 2 s 2 2p 3 4 S, 2 D and 2 P . T h e 2 D l e v e l h a s a v e r y
s m a l l r a d i a t i v e t r a n s i t i o n p r o b a b i l i t y and e f f e c t s of c o l l i s i o n a l d e - a c t i v a t i o n
a r e often i m p o r t a n t . The t r a n s i t i o n 2D 4
S g i v e s two c o m p o n e n t s , 2 D 3 / 2 -» 4
X 3726 and 2 D 5 / 2 -» 4 S X 3729. T h e i n t e n s i t y r a t i o f o r t h e s e two c o m p o n e n t s
c a n be c a l c u l a t e d allowing f o r a l l e l e c t r o n - i m p a c t and r a d i a t i v e t r a n s i t i o n s .
F o r N e i n t h e r a n g e 1(T to 10 t h e r a t i o i s s e n s i t i v e to N e , and f r o m m e a s u r i
r a t i o s Ne c a n b e d e d u c e d .
No e x p e r i m e n t a l d a t a a r e a v a i l a b l e f o r t h e c r o s s - s e c t i o n s f o r e x c i t a t i o n
of t h e f o r b i d d e n l i n e s . A g r e a t d e a l of e f f o r t h a s b e e n p u t into t h e a t t e m p t
to m a k e a c c u r a t e q u a n t u m - m e c h a n i c a l c a l c u l a t i o n s .
The radio s p e c t r u m . T h e r a d i o c o n t i n u u m i s due to
H + + e » H + + e + hv (3 .34)
S i n c e the electrons h a v e a M a x w e l l d i s t r i b u t i o n , K i r c h h o f f ' s l a w m a y be

a s s u m e d , (j v /K. v ) = B u ( T e ) ( s e e s e c t i o n 1). At r a d i o w a v e l e n g t h s ,
h v / ( k T e ) « 1 and B„ = (2 i / 2 / c 2 ) k T e (we h e r e u s e e n e r g y u n i t s , n o t q u a n t a ) .
T h e a b s o r p t i o n c o e f f i c i e n t f o r (3.34) can be c a l c u l a t e d f r o m c l a s s i c a l
e l e c t r o d y n a m i c s ( q u a n t u m c o r r e c t i o n s a r e s m a l l ) . It i s found t h a t Kv
b e h a v e s l i k e v"2 and b e c o m e s l a r g e f o r v s m a l l . We h a v e t h e r e f o r e to
c o n s i d e r t h e s o l u t i o n of a r a d i a t i v e t r a n s f e r p r o b l e m , to o b t a i n
I„ = B „ ( l - e~T") (3.35)
w h e r e т„ i s the o p t i c a l d e p t h along the line of s i g h t ,
T,V (3.36)
280 SEATON
T h e r e a r e two l i m i t i n g c a s e s . For v large, т i s s m a l l and
LV = BVTV = Bt K„di = j„df (3.37)
the o b s e r v e d i n t e n s i t y i s j u s t the e m i s s i o n i n t e g r a t e d along the line of s i g h t .

Since KV b e h a v e s like v"2, and B„ like v2, is approximately independent
of v ( s t r i c t l y s p e a k i n g it h a s a l o g a r i t h m i c f r e q u e n c y d e p e n d e n c e ) .
T h e second l i m i t i n g c a s e i s v s m a l l , rv l a r g e and
(3.38)
F r o m t h e o b s e r v e d s u r f a c e b r i g h t n e s s , T e c a n be d e d u c e d , but it i s
e s s e n t i a l to have m e a s u r e m e n t s with good a n g u l a r r e s o l u t i o n .
The a t o m i c r a d i o l i n e s , which a r e s i m i l a r to the r e c o m b i n a t i o n l i n e s
o b s e r v e d in t h e o p t i c a l r e g i o n , w e r e d i s c u s s e d at s o m e length by the a u t h o r
at the 1971 S t i r l i n g S u m m e r School. We s h a l l t h e r e f o r e d i s c u s s t h e m m u c h
more briefly here.
The t h r e e i m p o r t a n t f e a t u r e s a r e :
(i) It h a s b e e n s e e n t h a t a p p r e c i a b l e o p t i c a l d e p t h s c a n o c c u r in the r a d i o
c o n t i n u u m . A t r a n s f e r e q u a t i o n m u s t t h e r e f o r e be solved f o r the r a d i o l i n e s .
(ii) S t i m u l a t e d e m i s s i o n of line r a d i a t i o n by continuum r a d i a t i o n ,
H(n) + hv n n . H(n') + hi/ nn . + hy nn . (3.39)
c a n be i m p o r t a n t . T h i s i s b e c a u s e one h a s a c o m p a r a t i v e l y i n t e n s e r a d i a t i o n
f i e l d , and b e c a u s e the u p p e r l e v e l (n) i s o v e r p o p u l a t e d r e l a t i v e to the l o w e r
l e v e l (n 1 ), a s c o m p a r e d with the p o p u l a t i o n s in t h e r m o d y n a m i c e q u i l i b r i u m .
T h i s o v e r p o p u l a t i o n i s b e c a u s e a t o m s r e a c h the l e v e l s c o n c e r n e d due to
r e c o m b i n a t i o n . In o r d e r to c a l c u l a t e the a m o u n t of s t i m u l a t e d e m i s s i o n
( m a s e r action) a c c u r a t e c a l c u l a t i o n s of l e v e l p o p u l a t i o n s have to be m a d e ,
taking a l l r a d i a t i v e and c o l l i s o n a l e f f e c t s into a c c o u n t ,
(iii) P r e s s u r e b r o a d e n i n g of t h e l i n e s c a n be i m p o r t a n t . In e s s e n c e , the
m e c h a n i s m i s i n e l a s t i c e l e c t r o n - a t o m c o l l i s i o n s , which r e d u c e the d u r a t i o n
of t h e wave t r a i n and hence i n c r e a s e the width of the line ( i . e . of the p r o f i l e
f a c t o r <p(v) d i s c u s s e d in s e c t i o n 1).
A s an e x t r e m e c a s e , we c a n c o n s i d e r the line 220 a , o b s e r v e d in m a n y
d i f f u s e n e b u l a e . T h i s i s due to t h e t r a n s i t i o n 221 220. The width of the
o b s e r v e d line i s not m u c h g r e a t e r than the e x p e c t e d D o p p l e r width. T h i s
m e a n s that the e m i t t i n g r e g i o n m u s t have N e not m u c h l a r g e r than 10 2 cm" 3 .
The n e b u l a e c o n c e r n e d have s o m e r e g i o n s of m u c h h i g h e r density and t h e s e
give s t r o n g c o n t i n u u m r a d i a t i o n . The o b s e r v e d line m u s t t h e r e f o r e be
p r o d u c e d by m a s e r a c t i o n in o u t e r r e g i o n s of low d e n s i t y . At t h e s e low
d e n s i t i e s c o l l i s i o n a l e f f e c t s a r e s m a l l and d e p a r t u r e s f r o m t h e r m o d y n a m i c a l
e q u i l i b r i u m will be l a r g e ; m a s e r action will t h e r e f o r e be v e r y e f f e c t i v e .
I A E A - S M R - 1 2 / 4 4 , 4 6 , 48 2 8 1
BIBLIOGRAPHY
SECTION 1
Books
UNSOLD, A . , "Physik der S t e r n a t m o s p h ä r e n " , Springer ( 1 9 5 5 ) .
WOOLLEY, R . v . d . R . , STIBBS, D . W . N . , " T h e o u t e r l a y e r s of a s t a r " . O x f o r d ( 1 9 5 3 ) .
MIHALAS, D . , " S t e l l a r A t m o s p h e r e s " , F r e e m a n ( 1 9 7 0 ) .
SWIHART, T . L . , "Astrophysics a n d S t e l l a r A s t r o n o m y " , W i l e y ( 1 9 6 8 ) .
Review a r t i c l e s
HUMMER, D . G . , RYBICK1, G . , " T h e f o r m a t i o n of s p e c t r a l l i n e s " , A n n . Rev. A s t r o n . Astrophys. 9 , (1971) 2 3 7 .
PAGEL, B . E . J . , " A t o m i c c o l l i s i o n s and l o c a l t h e r m o d y n a m i c e q u i l i b r i u m in s t e l l a r a t m o s p h e r e s " , Proc.

R. S o c . A 3 0 6 ( 1 9 6 8 ) 9 1 .
Pressure b r o a d e n i n g
PAGEL, B . E . J . , " T h e i m p o r t a n c e of s p e c t r a l l i n e s h a p e s in a s t r o p h y s i c s " , J. Phys. B: A t o m , m o l e c . Phys.

4 (1971) 2 7 9 .
VAN REGEMORTER, H . , "Spectral line broadening", Stirling lectures (1971).
Hot stars
AUER, L . H . , MIHALAS, D . , " N o n - L T E M o d e l A t m o s p h e r e s " , Astrophys. J. S u p p l . 2 4 (1972) 1 9 3 .

MIHALAS, D . , HUMMER, D . G . , " A n a l y s e s of l i g h t - i o n s p e c t r a in s t e l l a r a t m o s p h e r e s . I l l , N i t r o g e n III
in t h e О s t a r s " , A s t r o p h y s . J . 179 (1973) 8 2 7 .
SECTION 2
Books
BILLINGS, D . E . , "A G u i d e to t h e Solar C o r o n a " , A c a d e m i c Press ( 1 9 6 6 ) .
ZIR1N, H . , " T h e Solar A t m o s p h e r e " , Blaisdell ( 1 9 6 6 ) .
SHKLOVSKY, I . S. , "Physics of t h e Solar C o r o n a " , P e r g a m o n (1966) ( t r a n s l a t e d f r o m Russian, 2nd e d i t i o n ( 1 9 6 2 ) ) .
S u m m e r School
"Physics of t h e solar c o r o n a " , N A T O A d v a n c e d Study I n s t i t u t e , A t h e n s ( 1 9 7 0 ) . MACRIS, C . J . , Ed. p u b l .

Reidel, Dordrecht-Holland (1971).
Review A r t i c l e s
SEATON, M . J . , " T h e s p e c t r u m of t h e solar c o r o n a " , P l a n e t a r y and S p a c e S c i e n c e 12_( 1964) 5 5 .
GABRIEL, A. H . , JORDAN, C . , " I n t e r p r e t a t i o n of s p e c t r a l i n t e n s i t i e s f r o m l a b o r a t o r y a n d a s t r o p h y s i c a l p l a s m a s " .

C a s e S t u d i e s in A t o m i c C o l l i s i o n Physics 2 (1972) 2 1 1 . McDOWELL, M . R . C . , McDANIEL, E . W . , Eds, N o r t h -
Holland Publ.
NEWKIRK, G . , " S t r u c t u r e of t h e solar c o r o n a " , A n n . Rev. Astron. Astrophys. 5 (1967) 2 1 3 .

2 8 2 SEATON
Ionization equilibrium
BURGESS, A , " D i e l e c t r o n i c r e c o m b i n a t i o n and t h e t e m p e r a t u r e of t h e solar c o r o n a " , Astrophys. J • 139

(1964) 7 7 6 .
JORDAN, C . , " I o n i z a t i o n e q u i l i b r i u m of e l e m e n t s b e t w e e n c a r b o n and n i c k e l " . Mon. N o t . R. Astr. S o c .

142 (1969) 5 0 1 .
SUMMERS, H . P . , " T h e d e n s i t y - d e p e n d e n t i o n i z a t i o n b a l a n c e for c a r b o n , o x y g e n and n e o n in t h e solar

atmosphere", M o n . N o t . R. Astr. S o c . 158 (1972) 2 5 5 .
SECTION 3
Books
SPITZER, L . , " D i f f u s e m a t t e r in s p a c e " , I n t e r s c i e n c e ( 1 9 6 8 ) .
ALLER, L . H . , " G a s e o u s N e b u l a e " , C h a p m a n and Hall ( 1 9 5 6 ) .
DUFAY, J . , " N e b u l e u s e s g a l a c t i q u e s e t m a t i è r e i n t e r s t e l l a i r e " , A l b i n M i c h e l (1954) (English t r a n s l a t i o n ,

" G a l a c t i c N e b u l a e and i n t e r s t e l l a r m a t t e r " , H u t c h i n s o n ( 1 9 5 7 ) ) .
PIKELNER, S . , " P h y s i c s of i n t e r s t e l l a r s p a c e " , F o r e i g n L a n g u a g e s P u b l i s h i n g H o u s e , Moscow ( 1 9 6 1 ) .
Review A r t i c l e s
SEATON, M . J . , " P l a n e t a r y N e b u l a e " , Rep. P r o g . Phys. 2 3 (1960) 3 1 3 .
OSTERBROCK, D . E . , " P l a n e t a r y N e b u l a e " , A n n . Rev. A s t r o n . A s t r o p h y s . 2 (1964) 9 5 .
DIETER, N . H . , GOSS, W. M . , " R e c e n t w o r k o n t h e i n t e r s t e l l a r m e d i u m " , Rev. M o d . Phys. 3 8 ( 1 9 6 6 ) 2 5 6 .
SEATON, M . J . , " A t o m i c c o l l i s i o n p r o c e s s e s in gaseous n e b u l a e " , A d v . A t o m . M o l e c . Phys. 4 (1968) 3 3 1 .

DALGARNO, A . , M c C R A Y , R . A . , " H e a t i n g a n d i o n i z a t i o n of H I r e g i o n s " , A n n . Rev. A s t r o n . Astrophys.
10 (1972) 3 7 5 .
Recombination spectra
BROCKLEHURST, M . , " C a l c u l a t i o n s of t h e l e v e l p o p u l a t i o n s of t h e low l e v e l s of h y d r o g e n i c ions in g a s e o u s

n e b u l a e " , M o n . N o t . R. Astr. S o c . 1 5 3 (1971) 471; " T h e l i n e s p e c t r a of h e l i u m in g a s e o u s n e b u l a e " , ibid.
157 ( 1 9 7 2 ) 2 1 1 .
R a d i o Lines
BROCKLEHURST, M . , S E A T O N , M . J . , " O n t h e i n t e r p r e t a t i o n of r a d i o r e c o m b i n a t i o n l i n e o b s e r v a t i o n s " ,

M o n . N o t . R. A s t r . S o c . 157 (1972) 1 7 9 .
IAEA-SMR-12/32, 35
LASER THEORY
H. HAKEN
Institute of Theoretical Physics,
University of Stuttgart,
Stuttgart, Federal Republic of Germany
Abstract
LASER THEORY.
1 . Gross f e a t u r e s of l a s e r l i g h t ; 1.1. Basic f e a t u r e s of t h e l a s e r ; 1 . 2 . The rate-equation approach;
Mode selection: s u r v i v a l of the f i t t e s t ; 1.3. The semi-classical approach; Intensities and frequency
s h i f t s of t h e solid s t a t e l a s e r ; T h e gas laser. 1 . 4 . Pulse p r o p a g a t i o n ; 2. Q u a n t u m t h e o r y of t h e l a s e r ;
2 . 1 . H a m i l t o n i a n and q u a n t u m - m e c h a n i c a l Langevin equations; 2 , 2 . Analogy with phase transitions.
1. GROSS F E A T U R E S O F L A S E R L I G H T
1.1. B a s i c f e a t u r e s of the l a s e r
T h e l a s e r d e v i c e i s e s s e n t i a l l y given by t h r e e e l e m e n t s : the " a c t i v e "

m a t e r i a l , t h e e n d - m i r r o r s and t h e p u m p ( s e e F i g . 1). What we a r e
u l t i m a t e l y i n t e r e s t e d in a r e t h e p r o p e r t i e s of t h e e m i t t e d l i g h t , i . e . : i t s
directionality; its intensity; its f r e q u e n c y ; its s p e c t r a l purity (linewidth),
or, more generally, its coherence properties.
A s we s h a l l s e e , t h e p r o p e r t i e s of l a s e r l i g h t d i f f e r e n o r m o u s l y f r o m
l i g h t f r o m o r d i n a r y s o u r c e s . L a s e r l i g h t i s d i r e c t i o n a l to s u c h a n e x t e n t
t h a t w h e n e m i t t e d f r o m t h e e a r t h i t c o v e r s only a c i r c l e of about 500 m
d i a m e t e r on t h e m o o n .
L a s e r l i g h t m a y a c h i e v e i n t e n s i t i e s of 10 12 W ( m o r e t h a n a l l t h e p o w e r
p l a n t s of t h e USA t o g e t h e r ) . L a s e r l i g h t m a y be p r o d u c e d f r o m t h e i n f r a r e d
to t h e u l t r a v i o l e t . Its s p e c t r a l p u r i t y c o m e s i n t o an o r d e r of m a g n i t u d e of
Avjv = 10" 1 5 . It m a y be p r o d u c e d in u l t r a - s h o r t p u l s e s of 10" 1 2 s d u r a t i o n .
F i r s t we s h a l l e x p l a i n s e v e r a l of t h e s e f e a t u r e s q u a l i t a t i v e l y :
(a) t h e a c t i v e m a t e r i a l m a y c o n s i s t , f o r e x a m p l e , of g a s a t o m s ,
i m p u r i t y a t o m s in a s o l i d m a t r i x , o r s e m i c o n d u c t o r s . We c o n s i d e r a s an
e x a m p l e f i x e d a t o m s w i t h t h r e e e n e r g y l e v e l s E 1 ; E 2 , E 3 ( F i g . 2). At r o o m
t e m p e r a t u r e , t h e a t o m s a r e in t h e i r g r o u n d s t a t e s . By K a s t l e r ' s m e t h o d
of o p t i c a l p u m p i n g t h e y a r e b r o u g h t to E 3 . F r o m t h e r e they a r e s u p p o s e d
to d e c a y q u i c k l y to E 2 . We a s s u m e t h a t t h e n u m b e r , N 2 , of a t o m s in
s t a t e 2 i s g r e a t e r t h a n t h e n u m b e r , N 1 ( of a t o m s in t h e g r o u n d s t a t e ,
N 2 > NJ. If the a t o m s a r e now h i t by l i g h t - q u a n t a w i t h a r e s o n a n t f r e q u e n c y
u = ( E 2 - E 1 ) / h t h e p r o c e s s of " s t i m u l a t e d e m i s s i o n " s t a r t s and an a v a l a n c h e
of q u a n t a i s p r o d u c e d , w h i c h l e a d s to v e r y h i g h e m i s s i o n p o w e r .
(b) T h e e n d - m i r r o r s s e r v e in t w o w a y s f o r t h e s e l e c t i o n of l i g h t q u a n t a ,
n a m e l y w i t h r e s p e c t t o d i r e c t i o n a l i t y , a s i l l u s t r a t e d in F i g . 3 , and with
r e s p e c t to t h e i r f r e q u e n c i e s , a s i l l u s t r a t e d in F i g . 4. F r o m F i g . 3 we
e x p e c t an e m i s s i o n p a t t e r n l i k e t h a t of F i g . 5. Of c o u r s e , t h e d u a l i t y
p h o t o n - w a v e m u s t be t a k e n i n t o a c c o u n t , w h i c h l e a d s to a f i n i t e d i f f r a c t i o n :
t h e a n g l e given by ip oc X/D, w h e r e D i s the m i r r o r d i a m e t e r . F r o m F i g . 4
we e x p e c t only d i s c r e t e f r e q u e n c i e s to be. p i c k e d out of a b r o a d e n e d a t o m i c
e m i s s i o n l i n e , a s s h o w n in F i g . 6.
283
2 8 4 HAKEN
PUMP-LIGHT
ACTIVE MATERIAL
-MIRRORS -
FIG. 1. S c h e m a t i c d i a g r a m of l a s e r d e v i c e .
QUICK DECAY
PUMP
DESIRED RADIOATIVE
DECAY
HE,
FIG.2. Lasing atom with three energy l e v e l s .
FIG.3. End m i r r o r s for l i g h t - q u a n t a s e l e c t i o n ; l i g h t q u a n t a e m i t t e d in a x i a l d i r e c t i o n h a v e g r e a t e r l i f e t i m e s .
E
7/ u к j /
/ 2 ' /
// /
У
A
A,
/ £
У £
FIG.4. O n l y q u a n t a w i t h d i s c r e t e f r e q u e n c i e s v^, m2i . . . i'n . . . a r e a l l o w e d s i n c e v ~ c / X a n d n V 2 = L or

wn - n c / 2 L , n b e i n g a n i n t e g e r .
I A E A - S M R - 1 2 / 4 4 ,46,48 2 8 5
FIG. 5 . Expected emission pattern.
FIG.6. S e l e c t i o n of d i s c r e t e f r e q u e n c i e s by the m i r r o r s .
286 HAKEN
T h e c o h e r e n c e p r o p e r t i e s m a y be " u n d e r s t o o d " a s f o l l o w s :
(1) An o r d i n a r y l a m p , w h e r e the r a n d o m e m i s s i o n of w a v e - t r a c k s
t a k e s p l a c e with no p h a s e r e l a t i o n , a s i l l u s t r a t e d in F i g . 7.
(2) The l a s e r , w h e r e the e m i s s i o n conditions a r e as i l l u s t r a t e d in F i g . 8.
1.2. The r a t e equation a p p r o a c h
[Rate e q u a t i o n s f o r p h o t o n s w e r e i n t r o d u c e d by E i n s t e i n . In connection
with l a s e r s , they w e r e f i r s t i n t r o d u c e d by H. Statz and G. A. de M a r s , 1 9 6 0 ] .
We t r e a t a s i n g l e m o d e with n p h o t o n s , and t w o - l e v e l a t o m s with
o c c u p a t i o n n u m b e r s Nj, N 2 of the l e v e l s one and two, r e s p e c t i v e l y . The
t e m p o r a l change of n, i . e . d n / d t , i s c a u s e d by:
(1) s p o n t a n e o u s e m i s s i o n : WN 2 , w h e r e W d e n o t e s t h e s p o n t a n e o u s decay
r a t e of a s i n g l e a t o m
(2) s t i m u l a t e d e m i s s i o n : N2 Wn
(3) a b s o r p t i o n : - N j Wn
(4) l o s s e s of photons t h r o u g h end f a c e s e t c . : - 2K. n, w h e r e к i s the decay
c o n s t a n t , 2к = 1 /10 and t 0 i s the l i f e t i m e of the photon in the " c a v i t y " .
Hence
= WCNg-N^n + WN2-2Kn (2.1)
L a s e r a c t i o n s t a r t s , if the f a c t o r of n > 0, i. e.
W(N 2 - N : ) > 2k
We d e t e r m i n e W in t h e following way: If т i s the r a d i a t i o n l i f e t i m e of

an a t o m , then it e m i t s l / т p h o t o n s (of all kinds) p e r s e c o n d s p o n t a n e o u s l y .
B e c a u s e we a r e i n t e r e s t e d in only one s p e c i a l m o d e , we m u s t divide l / т
by p, the n u m b e r of m o d e s within the s p o n t a n e o u s line width Au of the a t o m :
W = 1/rp
where
p = 8 л-2 v 2 VAi//c 3
We t h u s obtain the f u n d a m e n t a l l a s e r condition of Schawlow and T o w n e s

(1958)
(N 2 - N-[)c3 1
8 т л-2 y 2 у д v to
In o r d e r to f u l f i l it, the following conditions m u s t be s a t i s f i e d :

(a) " c a v i t y " l i f e t i m e tQ l a r g e ,
(b) a t o m i c linewidth Av s m a l l ,
(c) i n v e r s i o n (N 2 - N x ) high: e f f i c i e n t o p t i c a l p u m p i n g .
I A E A - S M R - 1 2 / 4 4 ,46,48 287
Since N p N 2 m a y c h a n g e a s a r e s u l t of t h e l a s e r p r o c e s s , we m u s t a l s o
consider their corresponding rate equations:
^^NjWjj+NjWjs-lNî-NiJWn (2.3)
— 1 = N2 w 2 1 - N i w 1 2 + ( N a - N ^ W n (2.4)
Wjj a r e t r a n s i t i o n r a t e s due t o p u m p i n g and i n c o h e r e n t d e c a y . P u t t i n g

!N1 + N 2 = N (= t o t a l n u m b e r of a t o m s ) , we d e r i v e f r o m (2. 3) and (2. 4) f o r
D = N2-Ni:
f £ = ÛL_D. 2 D W n (2.5)
where
_ w 12 - w 21 1 _
D N 12 W21
o - w 1 2 + w 21 ' Y "
F o r the s t a t i o n a r y s o l u t i o n d n / d t = 0; d D / d t = 0 we o b t a i n
n = (D 0 W - 2 k ) / 4 T W k
w h e r e we have n e g l e c t e d t h e s p o n t a n e o u s e m i s s i o n t e r m in (2. 1). As we

w i l l s e e l a t e r on, n i s t h e n u m b e r of " c o h e r e n t l y e m i t t e d p h o t o n s " ( s e e
a l s o F i g . 9).
SPONTANEOUS / STIMULATED
EMISSION / EMISSION
тнитпппнт
FIG. 9. C o h e r e n t e m i s s i o n of p h o t o n s .
FIG. 10. S p a t i a l d i s t r i b u t i o n of f i e l d s t r e n g t h U ( x ) .
2 8 8 HAKEN
L e t u s now c o n s i d e r the c a s e of m a n y m o d e s and m o d e s e l e c t i o n with

" s u r v i v a l of t h e f i t t e s t " ( f o r d e t a i l s s e e Haken (1970)). We now c o n s i d e r
s e v e r a l m o d e s which a r e d i s t i n g u i s h e d by an index X. The c o r r e s p o n d i n g
photon n u m b e r s a r e denoted by n x , t h e decay c o n s t a n t s by We f i r s t
p r e s e n t a m o r e e x a c t d i s c u s s i o n of the o p t i c a l t r a n s i t i o n r a t e W.
(a) It d e p e n d s on t h e s p a t i a l d i s t r i b u t i o n of t h e f i e l d s t r e n g t h U(x). T h e r e
i s no i n t e r a c t i o n at the n o d e s , but m a x i m u m i n t e r a c t i o n at the a n t i n o d e s
a s i l l u s t r a t e d in F i g . 10; g e n e r a l l y ,
2
Woe |и(х^)|
w h e r e х д d e n o t e s the p o s i t i o n of an a t o m with index ß.

(b) It d e p e n d s on t h e m o d e f r e q u e n c y and the a t o m i c f r e q u e n c y .
v f r e q u e n c y ( c i r c u l a r ) of atom ß
f r e q u e n c y ( c i r c u l a r ) of m o d e X
If a t o m i c line s h a p e i s L o r e n t z i a n with h a l f - w i d t h y (cf. F i g . 11),
FIG.11. Lorentzian a t o m i c line shape.
(с) It d e p e n d s on m o d e p o l a r i z a t i o n e x and a t o m i c t r a n s i t i o n dipole m o m e n t 0

j2
Using (a), (b), (c), we finally obtain t h e e x a c t f o r m of W^ (which

r e p l a c e s W)
2
K n - ^ T J ^ p k . x l (2.6)
where
(2.6a)
( T h i s e x p r e s s i o n w i l l be d e r i v e d exactly l a t e r . ) Let ( N 2 - N 1 ) f l b e the

i n v e r s i o n of a t o m ß, then we obtain f o r the field e q u a t i o n s :
I A E A - S M R - 1 2 / 4 4 ,46,48 289
(2.7)
M
sum over all atoms
stimulated emission spontaneous emission
The m a t t e r equations (two-level atoms) read
dN,
= W 12 N 1I(J - W 2 1 N 2 i ) j - ( Щ - Щ ) ^ N^wo, (2.8)
dt
X
dN = -w12Nli(J +w21N2i(J + ( N 2 - N 1 ) ( J ^ n x W ^ (2.9)
dt
w h e r e s u m m a t i o n i s c a r r i e d out o v e r a l l m o d e s .
T o find t h e s t e a d y - s t a t e s o l u t i o n , we put
d£!L = o- = о- ^ = 0 (2.10)
dt ' dt ' dt
and c o n s i d e r r u n n i n g w a v e s a s an e x a m p l e f o r m o d e s e l e c t i o n : In t h i s c a s e
| U x | = c o n s t ( s e e F i g . 12). We f u r t h e r a s s u m e t h a t a l l a t o m i c f r e q u e n c i e s a r e
t h e s a m e , v = v0, ( " h o m o g e n e o u s b r o a d e n i n g " ) . Thus
2T
W , W» (2.11)
" 72 + К - WX)2
SELECTION OF ONE
DIRECTION OF
PROPAGATION
ACTIVE MATERIAL
FIG. 12. Device producing running waves.
We put
(N2"Ni)fi = ( N a - N J
and o b t a i n a s f i e l d e q u a t i o n s f o r t h e s t e a d y s t a t e :
0 = -2Kxnx+nxW® ( N a - N ^ (2.12)
In t h e s e e q u a t i o n s s p o n t a n e o u s e m i s s i o n h a s b e e n n e g l e c t e d .
2 9 0 HAKEN
We t r e a t the e x a m p l e of two m o d e s , X = 1 , 2 , w h e r e
W°!
(2.13)
2
but let u s a s s u m e
Л!^0, n 2 =É0 (2.14)
F r o m (2. 12) it f o l l o w s : ( N 2 - N x ) = 2* X /W° f o r X = 1 and 2 in c o n t r a d i c t i o n

to (2. 13).
T h u s our a s s u m p t i o n (2. 14) was w r o n g ; only one n^ can be n o n - z e r o ,
the other m u s t vanish.
O u r r e s u l t m a y be e a s i l y g e n e r a l i z e d to the c a s e of m a n y m o d e s : Out
of t h e m only one m o d e with the h i g h e s t l i f e t i m e 1/2k. x and the g r e a t e s t
" g a i n " W^ s u r v i v e s , all o t h e r s v a n i s h .
T h i s r e s u l t h a s , by the way, v e r y i n t e r e s t i n g c o n s e q u e n c e s in biology,
w h e r e it j u s t d e s c r i b e s the s e l e c t i o n of s p e c i e s . 1
M o d e s m a y c o e x i s t , h o w e v e r , if the m o d e s a r e s p a c e - d e p e n d e n t o r
if t h e a t o m i c line i s i n h o m o g e n e o u s l y b r o a d e n e d .
M0DE1 MOOE 2
FIG. 13. Space-dependent modes.
FIG. 14. Two separated atomic lines.
1
Laser e q u a t i o n s w e r e proposed for b i o l o g i c a l p r o c e s s e s ( H a k e n , 1969 in M a r o i s : From theoretical
p h y s i c s to b i o l o g y ) and a p p l i e d to s e l e c t i o n a n d e v o l u t i o n of b i o l o g i c a l m o l e c u l e s by E i g e n in 1 9 7 1
(Naturwissenschaften).
I A E A - S M R - 1 2 / 4 4 ,46,48 291
T h e c a s e of s p a c e - d e p e n d e n t m o d e s i s s c h e m a t i c a l l y i l l u s t r a t e d in
F i g . 13. A p p a r e n t l y a t o m s in r e g i o n I s u p p o r t e s s e n t i a l l y m o d e 2, w h e r e a s
a t o m s in r e g i o n s II s u p p o r t e s s e n t i a l l y m o d e 1. T h u s d i f f e r e n t m o d e s a r e ,
roughly s p o k e n , s u p p o r t e d by d i f f e r e n t a t o m s . T h e y do not m u c h c o m p e t e
with e a c h o t h e r in " e a t i n g up" the a t o m i c i n v e r s i o n and thus can c o e x i s t .
The c a s e of i n h o m o g e n e o u s b r o a d e n i n g i s s k e t c h e d in F i g . 14. If the
c e n t r e l i n e s a r e d i f f e r e n t , m o d e s at the c o r r e s p o n d i n g f r e q u e n c i e s can be
supported simultaneously.
1.3. The s e m i c l a s s i c a l a p p r o a c h
(a) T h e field e q u a t i o n s
F r o m M a x w e l l ' s equation
c u r l H = 4 ITJ / с + ( E + 4 IT P) / с (3.1)
and u s i n g the r e l a t i o n s
J=aE; H = c u r l A; E = - A / c (3.2)
and the C o u l o m b gauge
div A = 0 (3. 3)
we obtain a d i f f e r e n t i a l equation f o r the v e c t o r p o t e n t i a l Â
. д д + с | 1 + ^ P (3.4)
and, by d i f f e r e n t i a t i o n with r e s p e c t to t i m e , an equation f o r the e l e c t r i c

field s t r e n g t h :
-AÊ+Jj l + ? (3.5)
(b) The m a t e r i a l e q u a t i o n s
We c o n s i d e r lasery a t o m s at fixed p o s i t i o n s , x^, with dipole m o m e n t s

рд. The p o l a r i z a t i o n P ( x ) i s then given by
P ( x ) = ^ 6(x - X(J ) P(J (3.6)

M
In a p u r e l y c l a s s i c a l p i c t u r e ( u s u a l d i s p e r s i o n t h e o r y ) p p obeys t h e equation
2
+ 2
WM + = ^ Е(3 М ) (3.7)
7 : a t o m i c width, i^: a t o m i c r e s o n a n c e f r e q u e n c y . T h i s equation d o e s not

account f o r s a t u r a t i o n . The c o r r e c t equation ( d e r i v e d l a t e r ) m u s t r e a d :
pM + 27ft, + i ^ p , , = - 2 u 0 (3.8)
292 HAKEN
w h e r e d^ = (N 2 - Nj)^: a t o m i c i n v e r s i o n , u 0 : a v e r a g e m o d e f r e q u e n c y , @12:
atomic dipole-moment m a t r i x element.
(We a s s u m e d 0 1 2 , pM, E to be p a r a l l e l ) . We m u l t i p l y E q . ( 3 . 8 ) and s u m up
o v e r M: ( a s s u m i n g i/ц = v)
|2
P ( x , t ) + 27 P (x, t) + v 2 P ( ï , t ) = - 2 u 0 -' Q * 21 Ě (x) d (x) (3.9)
where
d(x) = ; б (x - x ^ J d ^
M
F o r the r a t e of c h a n g e of e n e r g y of t h e a t o m s we find
^(tivdp) (hvd|,) f i e l d (h V d^reiaxation (3.10)
where
d
Aield = 2Е(Зм)р, (3.11)
i s t h e u s u a l c l a s s i c a l e x p r e s s i o n f o r an o s c i l l a t o r . F o r a two-level atom
the relaxation t e r m r e a d s
d ( h v d u ) \ _ h v ( d n - d ) u
(3.12)
dt / relax. T
w h e r e d 0 i s t h e e q u i l i b r i u m v a l u e and T i s the r e l a x a t i o n t i m e .
E q s (3. 10), (3. 11), (3. 12) yield
o r , a f t e r m u l t i p l i c a t i o n with б ( х - х р ) and s u m m a t i o n o v e r ц:
± d(x) - Ü L ^ H x ) + 2_ e ( 5 ) | 5 ( 3 ) (3 _14)
E q s (3. 5), (3. 9), (3. 14) a r e good f o r d e s c r i b i n g both l a s e r p h e n o m e n a and

p u l s e - p r o p a g a t i o n (7r-pulses, s e l f - i n d u c e d t r a n s p a r e n c y , e t c . ), a s l o n g a s
fluctuations a r e neglected.
(c) The mode picture
We e x p a n d E ( x , t ) i n t o n o r m a l i z e d " m o d e - f u n c t i o n s " Ux.(x) ( e . g . U (x)

~ s i n kx f o r s t a n d i n g w a v e s o r U (x) ~ exp(ikx) f o r r u n n i n g w a v e s ) :
E(x,t) Ex(t)Ux(x) (3.15)

\
IAEA- SMR- 1 2 / 3 2 , 35 2 9 3
T h e U v e c t o r s obey the h o m o g e n e o u s wave equation
дих (3.16)
I n s e r t i n g (3. 14) into (3. 5) we obtain a f t e r m u l t i p l i c a t i o n with U x and

i n t e g r a t i o n o v e r the v o l u m e :
<4 E x + Ёх+ 2к х E x = - 4 т г Р х (3.17)
where
= /UxcrUxdV
and
Px = / U x P x d V
T h e e x p a n s i o n (3. 15) m u s t be a l s o i n s e r t e d into (3. 8) and (3. 13).
(d) The r o t a t i n g - w a v e a p p r o x i m a t i o n
We put
Ex(t) = e x p í - i u x t j Ě P í t ) + e x p ( i u x t ) E x " > (t) = Ex <+) (t) + EjT> (t) (3.18)
F I G . 15. D e c o m p o s i t i o n of E x (t) i n t o a slowly v a r y i n g a m p l i t u d e E x (t) and a r a p i d l y v a r y i n g a m p l i t u d e

exp (iwxt).
F i g u r e 15 shows t h e d e c o m p o s i t i o n of E x ( t ) into a slowly v a r y i n g a m p l i t u d e

Ex(t) and a r a p i d l y v a r y i n g a m p l i t u d e е 1шх1 ; _ E v a r i e s m u c h m o r e slowly
than exp(iu x t). T h e r e f o r e we m a y n e g l e c t Ê c o m p a r e d to Еш к . A. s i m i l a r
t r e a t m e n t holds f o r р м . We t h u s obtain f r o m (3. 17), u s i n g (3. 18),
(3.19)
294 HAKEN
S i m i l a r l y we find
pf) = (iiv-TÎpjP +i Üx(2M)EjT4 (3-2°)

X
and
dл . - dл 9 i Г ш - /-•,
d = »- » + Ü 4+) U^S^p^-c.c. (3.21)
К T ft
v
X
We h a v e n e g l e c t e d t e r m s p r o p o r t i o n a l to e x p ( 2 i u t ) , w h i c h v a r y r a p i d l y and
a r e v a n i s h i n g l y s m a l l , if t h e y a r e a v e r a g e d o v e r a f i n i t e t i m e i n t e r v a l .
T h e s a m e a p p r o x i m a t i o n i s m a d e in t h e t h e o r y of s p i n r e s o n a n c e , w h e r e i t
is called the r o t a t i n g - w a v e approximation.
(e) Dimensionless quantities
In o r d e r to be l a t e r a b l e to m a k e d i r e c t c o n t a c t with t h e q u a n t u m -
t h e o r e t i c a l t r e a t m e n t we put
= - i j 2 * h u x bf
ЕГ) = E m
• P(i+) = 021 P21.M; = 012Pl2,M (3-22)

d N
M= 2,|j"Nl,M =
P22.il- Pu,(I
In t h e l a t e r q u a n t u m - m e c h a n i c a l t r e a t m e n t , b x , b+x a r e t h e a n n i h i l a t i o n and
c r e a t i o n o p e r a t o r s of p h o t o n s , and a r e t h e elements of t h e d e n s i t y m a t r i x
p = ( PH P
12 ]
P
\P21 22j
of t h e a t o m ß . We f u r t h e r i n t r o d u c e the c o u p l i n g c o n s t a n t g:
gM* = 1 0 2 1 ^ ( 5 ^ 2 ™ , / h (3.24)
(f) T h e c o m p l e t e s e t of s e m i c l a s s i c a l l a s e r - e q u a t i o n s
T h i s s e t a c q u i r e s , a f t e r the above quantities have been i n t r o d u c e d , the

following f o r m :
bx(t) = ( i u x - K x ) b £ ( t ) ëlxPn,^ <3-25>

p'
= -1
Р12,м^) (i^-TOPiz.M ^ g M x b x ( p 2 2 - Pn) M (3.26)
X
ď, +2ip21>(1^ g^bjf+G.c. (3.27)

I A E A - S M R - 1 2 / 4 4 ,46,48 295
T h e s e e q u a t i o n s apply to t w o - l e v e l a t o m s . H e r e d^ = ( p 2 2 - Р п ) м i s t h e
i n v e r s i o n of a s i n g l e a t o m . ( F o r e q u a t i o n s r e f e r r i n g to m u l t i - l e v e l a t o m s
s e e H a k e n (1970)).
(g) D e r i v a t i o n of t h e r a t e - e q u a t i o n s f r o m E q s (3. 25) - (3. 27)
E q u a t i o n s (3.25) - (3.2 7) c o n t a i n m o r e i n f o r m a t i o n t h a n t h e r a t e e q u a t i o n s ,
b e c a u s e t h e y r e f e r both t o a m p l i t u d e s and f r e q u e n c i e s . We now d e m o n s t r a t e ,
how t h e r a t e e q u a t i o n s f o l l o w and w h i c h a p p r o x i m a t i o n s m u s t be m a d e . .
We a s s u m e t h a t
b*(t) = B £ ( t ) e i s V (3.28)
w h e r e B j m a y be t r e a t e d a s p r a c t i c a l l y t i m e - i n d e p e n d e n t , w h i c h i s a l s o
a s s u m e d f o r ( p 2 2 - Р ц ) г T h e i n t e g r a t i o n of ( 3 . 2 6 ) t h u s y i e l d s :
0 = У - i g ^ ( P 2 2 - P n V Ь ф (3 29)
I n s e r t i n g (3. 29) i n t o (3. 25), m u l t i p l y i n g (3. 25) by b x and a d d i n g t h e c o m p l e x

c o n j u g a t e e q u a t i o n we f i n d :
n„ = - 2/4 П) + (Ряа-РпЬ bl''bx , (3. 30)

И X"
T h e r a t e e q u a t i o n s f o l l o w only if w e n e g l e c t t e r m s X' Ф X (by t h e a r g u m e n t ,

t h a t t h e p h a s e s b e t w e e n b x . and b x a r e u n c o r r e l a t e d . T h i s a r g u m e n t b r e a k s
d o w n , h o w e v e r , if t h e p h a s e s a r e l o c k e d by e x t e r n a l m e a n s ( " p h a s e - l o c k e d
l a s e r " ) ) . We o b t a i n
ňx = - 2 ^ x n x + ^ W X ( j ( N 2 - N ^ nx (3.31)
where
W, = I 2
T
i . e, in t h e f o r m of (2. 6) w i t h f 2 x i n s t e a d of шх; N 2i(J = p 2 2 N1 м = p n

E q . (3. 31) c o i n c i d e s w i t h (2. 7), if the s p o n t a n e o u s - e m i s s i o n t e r m i s
n e g l e c t e d . . I n s e r t i n g ( 3 . 2 9 ) i n t o ( 3 . 2 7 ) y i e l d s a r a t e e q u a t i o n f o r d^ =
( N ^ N ^ p , which is equivalent to (2.8), (2.9), provided
= w^-w^
0
w12 + w21
Y = w12 + w21 (3. 33)
(h) Method of s o l u t i o n of t h e e q u a t i o n s (3. 25) - (3. 27)
B e c a u s e t h e unknown v a r i a b l e s b'j;, p 1 2 , p 2 2 - Р ц o c c u r at s e v e r a l p l a c e s
in p r o d u c t s , t h e s e e q u a t i o n s a r e n o n l i n e a r and c a n n o t be s o l v e d e x a c t l y
296 HAKEN
(except f o r s p e c i a l c a s e s ) . We have t h u s developed a s e l f - c o n s i s t e n t field

a p p r o a c h with i t e r a t i v e s t e p s : (for convenience we t r e a t only a single
m o d e ) . The i n d i v i d u a l s t e p s a r e as follows:
1) We put d„ = d(uC) = d 0 (3. 34)
We s t a r t with the i n v e r s i o n given by (3. 32), i. e . n e g l e c t i n g l a s e r action.

We a s s u m e f u r t h e r that
bf = Bf exp (i ВД (3. 35)
w h e r e В* and a r e s t i l l to be d e t e r m i n e d s e l f - c o n s i s t e n t l y . L e t us now
i l l u s t r a t e the i t e r a t i o n p r o c e d u r e :
field b* = B * e x p ( i a t ) dipole
given; f r o m (3.26) (3.27)
i n v e r s i o n d„ = d. moment
inversion
dM = d „ - 11.1
(3. 26)
improved
new field
(3.25) -{ dipole m o m e n t 2
equation
P 1 2 ~ b * r b * | b |
2) Using ( 3 . 3 4 ) , (3. 35) in Eq. (3.26) y i e l d s ( a f t e r i n t e g r a t i o n )
ex
p12>(J -- - dH0 BR*
- gcrM (n_
P ( i ň t :) y ) (3. 36)
3) Using (3. 36) in (3. 27) y i e l d s an i m p r o v e d e x p r e s s i o n f o r the i n v e r s i o n
d,=d0 + 2i d 0 TlB|2[g,l 2
( ^.^. i T -c.c.
o r , a f t e r a s l i g h t r e a r r a n g e m e n t of the t e r m s ,
4 Y dp T I В 12 |g„|2
(V - d0 • (3.37)
( f i - 1/^)2+72
4) Using (3. 37) in (3, 26) y i e l d s
=- f d . 47d0T|B|2|gJ2 B* exp (i ň t )
0 (3. 38)
°12.м V о (S2- У / + 7 S =M ( f i - ^ - v y )
5) I n s e r t i n g (3. 38) into (3. 25) leads to the b a s i c s e l f - c o n s i s t e n t field

equation
•... ,. ..> . , V i ' 12 B* exp (i a t )

IAEA-SMR-12/44, 46 , 48 297
4
4 7 Т | в | 2 В* exp(iSît)
>1 I Sc|
Ц
(3. 39)
which h a s the following s t r u c t u r e
i П B* = (iu - к)В* - i d 0 B * Ci + i d 0 | в | 2 b
* c2 (3. 40)
w h e r e C 2 and C 2 a r e c o m p l e x c o n s t a n t s given by
3 4 1
( П - < - '
ß
C
2 = } , l g M l 4 4 T T ( ( П - I / )2 + y 2 ) ( n - „ - i T ) (3
-42)
ß
A f t e r dividing Eq. ( 3 . 4 0 ) by B*, we m a y s e p a r a t e the r e s u l t i n g equation into

r e a l and i m a g i n a r y p a r t s f r o m which we m a y d e t e r m i n e
U and I В I 2
The equation f o r n = | в | 2 h a s the following s t r u c t u r e :
2-е = G - Sn
If the a t o m i c line i s h o m o g e n e o u s l y b r o a d e n e d , v^ = v, one f i n d s a

" f r e q u e n c y pulling"
7 Ц + K V
П = v( 3 . 4 3 )
7 + к '
f i r s t d e r i v e d by Townes (1961).
The a c t u a l f r e q u e n c y of the l a s e r light thus d i f f e r s f r o m the f r e q u e n c y ы

of t h e m o d e in the " u n l o a d e d " cavity and the c e n t r e f r e q u e n c y v of the a t o m i c
line.
If the a t o m i c l i n e is i n h o m o g e n e o u s l y b r o a d e n e d , o t h e r " m o d e - p u l l i n g "

e f f e c t s o c c u r (Haken and S a u e r m a n n , 1963). The g e n e r a l c a s e of m a n y
m o d e s can be t r e a t e d along the s a m e l i n e s . The r e s u l t i n g s e l f - c o n s i s t e n t
field e q u a t i o n s then have the following s t r u c t u r e : 2
4 = bjí+X С ^ Д з ^ Л ^ з (3
-44)
Az Лз
The c o n s t a n t s С s t i l l depend on t h e m o d e - f r e q u e n c i e s . E q u a t i o n s ( 3 . 4 2 )
d e s c r i b e a n u m b e r of v e r y i n t e r e s t i n g e f f e c t s , which go beyond r a t e
e q u a t i o n s , e. g. m o d e l o c k i n g , e t c .
2
For d e t a i l s see H a k e n a n d S a u e r m a n n (1963) or H a k e n ( 1 9 7 0 ) .
298 HAKEN
S e m i c l a s s i c a l t r e a t m e n t of the g a s l a s e r
T h e r e a r e two m e t h o d s a v a i l a b l e , which a r e d i f f e r e n t in f o r m , but

e q u i v a l e n t ( H a k e n - S a u e r m a n n t r e a t m e n t and L a m b t r e a t m e n t ) . H e r e we
s k e t c h only the one t r e a t m e n t .
The e s s e n t i a l d i f f e r e n c e c o m p a r e d to the solid s t a t e l a s e r i s given h e r e
by the m o t i o n of the g a s a t o m s . C o n s e q u e n t l y , we have to r e p l a c e x(J by
Хд + Vjjt; VJJ : v e l o c i t y of the a t o m ц. T h e i n t e r a c t i o n c o n s t a n t g ^ between
the m o d e Л. and the a t o m ц t a k e s thus the f o r m :
T h e s u m m a t i o n o v e r ju r u n s in t h e c o r r e s p o n d i n g e q u a t i o n s o v e r the
p o s i t i o n s x y and the v e l o c i t i e s v^ (for which a B o l t z m a n n d i s t r i b u t i o n i s
a s s u m e d ) . F o r the s o l u t i o n of the e q u a t i o n s of m o t i o n we put again ( s i n g l e -
mode case):
b*(t) = B* exp (i a t )
and p e r f o r m the s a m e i t e r a t i o n s t e p s a s d e s c r i b e d b e f o r e . We find f o r the

photon d e n s i t y H:
The l a s t f a c t o r i s of s p e c i a l i n t e r e s t , b e c a u s e it r e p r e s e n t s the " L a m b d i p " .

If we plot n a s a f u n c t i o n of Q, t h i s function s h o w s a dip at fi = u 0 .
Historical remarks
The s e m i c l a s s i c a l e q u a t i o n s contain the field e q u a t i o n s and the m a t t e r

e q u a t i o n s . The field e q u a t i o n s a r e evidently M a x w e l l ' s e q u a t i o n s . The
difficulty a r i s e s with the m a t t e r e q u a t i o n s . Even if they a r e d e r i v e d f r o m the
S c h r ö d i n g e r e q u a t i o n , t h e a d e q u a t e d a m p i n g t e r m s m u s t be i n c o r p o r a t e d
(and d e r i v e d ) . T h i s had f i r s t been done by Bloch (1946) and Bloch and
W a n g s n e s s (1953) in the c a s e of m a g n e t i c spin r e s o n a n c e . H e r e the d e n s i t y
m a t r i x p r e f e r s to s p i n s , with t h e i n d i c e s 1,2 r e f e r r i n g to spin up o r down,
r e s p e c t i v e l y . The r e l e v a n c e of t h e Bloch e q u a t i o n s to the d e s c r i p t i o n of t h e
m a s e r h a s been r e c o g n i z e d by F e y n m a n , Vernon and H e l l w a r t h (1957).
L a s e r e q u a t i o n s f o r the m u l t i m o d e c a s e w e r e t r e a t e d by Haken u s i n g
the above i t e r a t i o n s c h e m e (1962, C o n f e r e n c e on O p t i c a l P u m p i n g at
H e i d e l b e r g ) . T h i s m e t h o d (and an equivalent one) w e r e applied by Haken
and S a u e r m a n n to t h e s o l i d s t a t e and g a s l a s e r (1963) (in p a r t i c u l a r ,
c o e x i s t e n c e and s u p p r e s s i o n of m o d e s , f r e q u e n c y s h i f t s ) . In 1963, L a m b
p r e s e n t e d h i s t h e o r y of t h e g a s l a s e r at t h e Q u a n t u m E l e c t r o n i c C o n f e r e n c e
in P a r i s , f o r a d e t a i l e d v e r s i o n see P h y s . Rev. (1964). Since t h e n , n u m e r o u s
p a p e r s a p p e a r e d on the s e m i - c l a s s i c a l t h e o r y of the l a s e r .
The following r e v i e w a r t i c l e s r e f e r to the t h e o r y :

P r o c e e d i n g s of t h e V a r e n n a S u m m e r School, 1963 and 1969
Q u a n t u m O p t i c s , E d s S. M. Kay and A. M a i t l a n d , A c a d e m i c P r e s s (1970)
E n c y c l o p e d i a of P h y s i c s , Vol. X X V / 2 c , S p r i n g e r - V e r l a g (1970).
I A E A - S M R - 1 2 / 4 4 ,46,48 299
1.4. P u l s e p r o p a g a t i o n and r e l a t e d p h e n o m e n a
In the p a s t y e a r s it b e c a m e m o r e and m o r e evident that Eqs (3.5),

(3. 9), (3. 14), o r t h e i r s i m p l i f i e d v e r s i o n s in t h e r o t a t i n g wave a p p r o x i m a t i o n ,
p o s s e s s solutions describing pulse propagation. Mostly, t h e r e exist close
a n a l o g i e s to p h e n o m e n a in spin r e s o n a n c e . Such p h e n o m e n a a r e :
s u p e r r a d i a n c e , 27r-pulses ( s e l f - i n d u c e d t r a n s p a r e n c y ) , 7r-pulses, p h o t o - e c h o ,
and s e l f - p u l s i n g of l a s e r s .
E,
X 7
E,
F I G . 16. A n a l o g y b e t w e e n a t w o - l e v e l a t o m a n d spin 1 / 2 in a c o n s t a n t m a g n e t i c f i e l d .
FIG. 17. Spin possessing c o m p o n e n t in x y - p l a n e .
FIG. 18. E l e c t r o n possessing d i p o l e m o m e n t .
ELECTRON IN GROUND STATE ¥>

ELECTRON IN EXCITED STATE
ELECTRON IN MIXED STATE
300 HAKEN
B e c a u s e m o s t of t h e s e p h e n o m e n a can be r a t h e r e a s i l y u n d e r s t o o d in
t h e c a s e of s p i n s we f i r s t e s t a b l i s h :
(a) the analogy between a t w o - l e v e l a t o m and spin \ (in a c o n s t a n t m a g n e t i c
field in z - d i r e c t i o n )
Spin Atom
State: Spin down \ E l e c t r o n in ground s t a t e
Wave f u n c t i o n : 4>\
State: spin up t E l e c t r o n in e x c i t e d s t a t e
Wave f u n c t i o n : s0(t)
( s e e F i g . 18). Spin b e h a v e s like ( s e e F i g s 16, 17, 19). When t h e e l e c t r o n
g y r o : when it r e t u r n s f r o m i t s r e t u r n s f r o m i t s u p p e r to i t s l o w e r
e n e r g e t i c a l l y h i g h e r p o s i t i o n to i t s l e v e l , t h e dipole m o m e n t o s c i l l a t e s
energetically lower position (see ( s e e F i g . 19b). T h i s o s c i l l a t i n g
F i g . 19a). B e c a u s e the spin i s e l e c t r i c dipole m o m e n t c a u s e s
c o n n e c t e d with a m a g n e t i c m o m e n t , radiation.
spin o s c i l l a t i o n s in the x y - p l a n e
cause radiation.
S u p e r r a d i a n c e in spin s y s t e m s S u p e r r a d i a n c e in a t o m i c s y s t e m s
(See F i g . 19c); a l l s p i n s r o t a t e in (See F i g . 19d); all e l e c t r o n s o s c i l l a t e
p h a s e e s t a b l i s h i n g a giant dipole in p h a s e ; h e n c e r e s u l t s a giant
moment e l e c t r i c dipole m o m e n t
P = Np P = Np
w h e r e N i s the n u m b e r of s p i n s and w h e r e N i s the n u m b e r of a t o m s and
p i s the dipole m o m e n t of individual p i s the dipole m o m e n t of i n d i v i d u a l
s p i n . The r a d i a t e d p o w e r ocP2, thus atom.
°cN2, i. e. a c o o p e r a t i v e e f f e c t . H e r e we have exactly the s a m e e f f e c t
(If s p i n s a r e not in p h a s e , the a s in t h e spin s y s t e m .
r a d i a t e d power °c N. ) B e c a u s e t o t a l
e n e r g y oc N, but a l s o к p o w e r • т
( t i m e ) (see F i g . 19e), we obtain f o r
the pulse duration
1
T<X
N
i. e. a v e r y s h o r t o u t b u r s t i s
obtained.
Spin echo Photo echo
Spins in l o c a l l y d i f f e r e n t m a g n e t i c A t o m s with d i f f e r e n t t r a n s i t i o n
f i e l d s o s c i l l a t e with d i f f e r e n t f r e q u e n c i e s have o s c i l l a t i n g dipole
f r e q u e n c i e s and get out of p h a s e m o m e n t s with d i f f e r e n t f r e q u e n c i e s .
( F i g . 19f). T h u s r a d i a t i o n v a n i s h e s H e r e the s a m e e f f e c t is o b s e r v e d .
a f t e r a s h o r t t i m e ; s e e F i g . 19g.
By an e x t e r n a l p u l s e the s p i n s a r e The s a m e e f f e c t i s o b s e r v e d f o r a t o m s
flipped a s i l l u s t r a t e d -in F i g . 19h. in a light f i e l d .
B e c a u s e they k e e p r o t a t i n g with T h i s e f f e c t w a s found in, f o r e x a m p l e ,
t h e i r o r i g i n a l s p e e d , they have ruby.
after a certain time their original
p o s i t i o n ( F i g . 19i). They now
s t a r t again to r a d i a t e in p h a s e , thus
e m i t t i n g an echo ( F i g . 19j).
IAEA-SMR-12/32, 35 3 0 1
( с )
(d)
(e) И)
X-Y PLANE
(h)
(j)
(i)
FIRST EXTERNAL ECHO

PULSE PULSE
FIG. 19. C o m p a r i s o n b e t w e e n spin o s c i l l a t i o n and d i p o l e - m o m e n t o s c i l l a t i o n ; (a) spin b e h a v i n g l i k e g y r o ;

(b) o s c i l l a t i n g e l e c t r i c d i p o l e m o m e n t ; (c) s u p e r r a d i a n c e in spin s y s t e m ; (d) e l e c t r o n s o s c i l l a t i n g i n p h a s e ;
(e) e m i s s i o n of p u l s e of d u r a t i o n r ; (f) spin e c h o ; (g) e m i s s i o n c u r v e ; (h) spin f l i p : (i) o r i g i n a l p o s i t i o n ;
(j) e m i s s i o n of e c h o .
302 HAKEN
-SWINGS
, l i l i ;
(а) Г
ITT
( b )
JLQ
STANDSTILL
O
ITS"
(с)
A * I
PUSH
1 1 i l г
( d ) I
AO , Q
FIG.20. M e c h a n i c a l a n a l o g u e of s e l f - i n d u c e d t r a n s p a r e n c y : I n c o m i n g pulse m e e t s s w i n g i n g a t o m s (a) w h i c h

b e c o m e e x c i t e d (b), ťhen f a l l b a c k t o ground s t a t e (c) a n d push ( d ) .
IAEA-SMR-12/32, 35 303
(b) Self-induced transparency
If u s u a l light h i t s a s y s t e m of a t o m s at a r e s o n a n c e f r e q u e n c y , it i s
a b s o r b e d . If t h e i n c o m i n g light p u l s e is s o s h o r t , t h a t i t s d u r a t i o n i s
s h o r t e r than t h e a t o m i c r e l a x a t i o n t i m e s and if it i s s u f f i c i e n t l y i n t e n s e ,
t h e m e d i u m b e c o m e s t r a n s p a r e n t . T h i s e f f e c t can b e s t be e x p l a i n e d by
a m e c h a n i c a l analogue i l l u s t r a t e d in F i g . 20. T h e m a n in t h e c a r t r e p r e s e n t s
the i n c o m i n g light p u l s e , the s w i n g s a r e t h e a t o m s in t h e i r ground s t a t e s
(Fig. 20a). The a t o m i s e x c i t e d when light i s a b s o r b e d ( F i g . 20b). The a t o m
f a l l s down into i t s ground s t a t e a s light i s e m i t t e d (Fig. 20c). The net e f f e c t
a f t e r a l l p u s h e s i s i l l u s t r a t e d in F i g . 2Od: The c a r t g o e s on with i t s o r i g i n a l
v e l o c i t y , but i t s v e l o c i t y within the s w i n g s w a s e f f e c t i v e l y m u c h s m a l l e r .
T h u s t h e light h a s been t r a n s m i t t e d at a c o n s i d e r a b l y d e c r e a s e d s p e e d .
FIG.21. S e l f - p u l s i n g in l a s e r s .
(c) S e l f - p u l s i n g in l a s e r s
If t h e i n v e r s i o n d 0 (in t h e s e m i c l a s s i c a l e q u a t i o n s ) i s s u f f i c i e n t l y high,
.the s i n g l e - m o d e s o l u t i o n b e c o m e s u n s t a b l e , and suddenly v e r y s h a r p
p u l s e s s t a r t to t r a v e l in the l a s e r ( F i g . 21).
It should be m e n t i o n e d that p a r t of the above p h e n o m e n a a r e c l o s e l y
r e l a t e d to (or m a t h e m a t i c a l l y even i d e n t i c a l with) s o l i t o n s , which a r e
s o l u t i o n s of n o n l i n e a r w a v e - e q u a t i o n s , r e t a i n i n g t h e i r f o r m .
The following a r e s o m e u s e f u l r e f e r e n c e s :
S u p e r r a d i a n c e : D i c k e , P h y s . R e v . (1954)
M o r e r e c e n t l y n u m e r o u s p a p e r s by A r e c c h i , B o n i f a c i o , H a a k e , R e h l e r ,
S c h w e n d i m a n n , E b e r l y , and o t h e r s , m o s t l y p u b l i s h e d in P h y s . Rev.
Photo-echo: A b e l l a , K u r n i t , and H a r t m a n n (1965) and o t h e r s .
Self-induced transparency: M c C a l l and Hahn (1967).
S e l f - p u l s i n g of l a s e r s : G r a h a m and Haken (1968) and, in p a r t i c u l a r ,
R i s k e n and N u m m e d a l (1968).
F o r a d e t a i l e d l i s t of r e f e r e n c e s s e e Haken (1970), p. 224.
3 0 4 HAKEN
2. QUANTUM THEORY O F T H E LASER
2.1. H a m i l t o n i a n and q u a n t u m - m e c h a n i c a l L a n g e v i n e q u a t i o n s
The H a m i l t o n i a n of the s y s t e m
The s y s t e m c o n s i s t s of l a s e r a t o m s and the e l e c t r o m a g n e t i c f i e l d :

both a r e coupled to t h e i r s u r r o u n d i n g s a s i l l u s t r a t e d in F i g . 22. T h u s the
total Hamiltonian must read
+
H =
H atoms H field + Hint_ a t .-f i e i d
+
Hheatb. (at.) +
H h e a t b. (field) proper laser (1)
system
+ + H
^bath-atoms bath-field
interaction interaction
FIG.22. Coupling b e t w e e n l a s e r a t o m s and e l e c t r o m a g n e t i c f i e l d .
The p r o p e r l a s e r s y s t e m
We d e c o m p o s e the v e c t o r p o t e n t i a l into cavity m o d e s U^(x):
A(2)=) ) ( 4 + b+*) U x (x) (2)

x
where
[bx.bjj=6xv etc. (3)
and
h
Hfleld = X "Abx (4)
We d e c o m p o s e the c r e a t i o n and a n n i h i l a t i o n o p e r a t o r s Ф (x), Ф + (х) of the

e l e c t r o n - w a v e field into a s e r i e s of a t o m i c wave f u n c t i o n s , d e s c r i b i n g
e l e c t r o n s at t h e a t o m ц in t h e l o w e r and u p p e r s t a t e , r e s p e c t i v e l y :
IAEA-SMR-12/32, 35 305
Ф (S) = Y a^j tyj (x) 3 = 1.2 (5)

M.J
Ф+ =£ 4 (3) (6)
f ,j
where
6 etc (7)
[ v =V JJ- -
T h e H a m i l t o n i a n of t h e t o t a l a t o m i c s y s t e m r e a d s
Hatom = X EMj 4 J '8>

M.i
w h e r e E Mj i s the e n e r g y of l e v e l j of a t o m ß . We c h o o s e E ^ = 0 and - h v.
Then
Hatom = ^ a Í2 aM2 (9)

M
T h e i n t e r a c t i o n H a m i l t o n i a n r e a d s (only t e r m s l i n e a r in A b e i n g c o n s i d e r e d )
Hint = / ApJ*(x) (10)
w h e r e p is the m o m e n t u m o p e r a t o r . I n s e r t i n g E q s (2), (5), (6) i n t o E q . ( 1 0 )

yields :
H = h
int X Ka+2 b
\ S ? x + (a+i a ^ b t g ^ l (11)
X.M
where
<a2 a l V = a
Î 2 aMl etC
'
© 12 i s t h e d i p o l e m a t r i x e l e m e n t .
Note t h a t " a n t i r e s o n a n t " t e r m s a 2 a-, b + ; a^ a 2 b a r e n e g l e c t e d in the
rotating-wave approximation.
I n s e r t i n g E q s (4), (9), and (11) i n t o E q . ( l ) , we o b t a i n t h e H a m i l t o n i a n
of t h e p r o p e r l a s e r s y s t e m . To get a quick i n s i g h t into t h e m e c h a n i s m of
l a s e r a c t i o n , t h e H e i s e n b e r g e q u a t i o n s of m o t i o n h a v e t u r n e d out to be
m o s t u s e f u l . T h e y a r e l i s t e d in T a b l e I on t h e l e f t hand s i d e . E q u a t i o n (12)
d e s c r i b e s t h e c h a n g e of t h e a m p l i t u d e of t h e f i e l d m o d e X due to t h e
o s c i l l a t i n g a t o m i c d i p o l e m o m e n t s , E q . ( 1 3 ) d e s c r i b e s t h e c h a n g e of t h e
a t o m i c d i p o l e m o m e n t s d u e t o t h e f i e l d with a given i n v e r s i o n , (14) f i n a l l y
d e s c r i b e s the c h a n g e of t h e i n v e r s i o n . T h e r i g h t hand s i d e of T a b l e I
r e p r e s e n t s t h e e f f e c t s of t h e r e s e r v o i r s on t h e p r o p e r l a s e r s y s t e m . We
f i n d d a m p i n g t e r m s , w h i c h we h a d c o n s i d e r e d a l s o in t h e s e m i c l a s s i c a l
3 0 6 HAKEN
T A B L E I. QUANTUM-MECHANICAL LANGEVIN EQUATIONS O F THE

LASER
Proper system: H = Hat + Hjield + H

int
E f f e c t s of h e a t b a t h s
H e i s e n b e r g Eqs: Г2 [H,£2]
damping fluctuations
+
(12) t>l 1 £ g*\(4 a,) M "KXbX «
(13) ( а г »i)J, = i f ( a j - а г -T(4 a0M + Г

f 8 ~a* a
'V, 21,м«
do - o u
(14) 2
= i (aî а
г>д b+x - g * x Ú 4 b
x) T
+ Г
о,м(Ч
t h e o r y , but in addition a l s o f l u c t u a t i n g " f o r c e s " . If we d i s r e g a r d the f a c t

that t h e s e " f o r c e s " a r e o p e r a t o r s , the e q u a t i o n s of T a b l e I a r e of the
type of c l a s s i c a l L a n g e v i n e q u a t i o n s in s t a t i s t i c a l m e c h a n i c s .
To e l u c i d a t e the p h y s i c a l c o n s e q u e n c e s of the e q u a t i o n s of Table I,
we c o n s i d e r a s p e c i a l e x a m p l e :
Only one m o d e of i n f i n i t e w a v e l e n g t h : gMx = c o n s t = g;
e x a c t r e s o n a n c e between f i e l d m o d e and a t o m s : u = v.
We m a k e the t r a n s f o r m a t i o n : b+ b+ e l w t and i n t r o d u c e a-^ (a 2 a ^ ,Me lOJt
"
etc.
M
s =
M
L
Г etC s d
Г
21 =I 21.м - 0 0
.We find
b+ = - /с b+ + ig S+ + F +
Š+ = - 7 S+ - ig b+ S + Г 2 1 (15)
+2ig(S"b+ -bS+) +Fo
We now u s e the a d i a b a t i c a p p r o x i m a t i o n , which a s s u m e s that S + and S r e l a x

m u c h m o r e slowly in the coupled s y s t e m ( f i e l d - a t o m s ) than in the " f r e e "
a t o m i c s y s t e m which i s only coupled to the r e s e r v o i r s
S+ « y S+
IAEA- S M R - 1 2 / 32, 3 5 307
We t h u s obtain
S+=i(-igb+S+r2l)
and (16)
S = S 0 + 2 ig T (S" b+ - b S+) + T r o
and ( a f t e r s o m e r e a r r a n g e m e n t s )
b+ = b +
(^S 0 -Kj-4g2lTb +
b b+ + F t o t (t) (17)
E q . ( 1 7 ) can be i n t e r p r e t e d a s the equation of a p a r t i c l e m o v i n g (heavily

d a m p e d ) in the p o t e n t i a l ( s e e F i g . 23):
V(|b|) s,V — +
t K T | b |
FIG. 2 3 . S t r o n g l y d a m p e d p a r t i c l e m o t i o n in a p o t e n t i a l .
To d i s c u s s the r o l e of the t o t a l f l u c t u a t i n g f o r c e F t o t (t), we u t i l i z e it

in the following f o r m (which m a y a l s o be r i g o r o u s l y d e r i v e d )
(t) ôit-t^é 1<п

i
It t h u s r e p r e s e n t s p u s h e s at r a n d o m t i m e s t j with r a n d o m p h a s e s (py L e t
us now d i s c u s s the joint action of the f o r c e with the p o t e n t i a l V( | b | ) and the
f l u c t u a t i n g f o r c e F . We t r e a t b a s if it w e r e a c l a s s i c a l v a r i a b l e . Again
t h i s p r o c e d u r e m a y be j u s t i f i e d in d e t a i l ( s e e H a k e n , 1970). F o r s m a l l
p u m p i n g , i . e . a s m a l l i n v e r s i o n S 0 , t h e s y s t e m i s below t h r e s h o l d w h e r e
— S 0n - к. < 0
7
B e c a u s e | b | i s s m a l l , the n o n l i n e a r i t y in V ( | b | ) m a y be n e g l e c t e d . A f t e r
e a c h p u s h (by F (t)) the " p a r t i c l e " c o m e s down the p o t e n t i a l c u r v e , b i s
t h u s a s u p e r p o s i t i o n of e x p o n e n t i a l f u n c t i o n s
308 HAKEN
e-?< t_t j> ; t š tj
where
2
£
7 =к- — S
7
Going back to the l a n g u a g e of m o d e a m p l i t u d e s , t h i s r e s u l t m a y be i n t e r -

preted as follows:
T h e field c o n s i s t s of d a m p e d wave t r a c k s ccexp(--ýt). If the t e m p o r a l

b e h a v i o u r of t h e m o d e i s F o u r i e r analyzed by a s p e c t r o g r a p h , y gives r i s e
to the o p t i c a l line width. B e c a u s e y d e c r e a s e s with i n c r e a s i n g i n v e r s i o n S 0 ,
a l i n e - n a r r o w i n g o c c u r s . B e c a u s e the wave t r a c k s a r e s u p e r i m p o s e d
i n d e p e n d e n t l y , the t o t a l field a m p l i t u d e (b) p o s s e s s e s a G a u s s i a n d i s t r i b u t i o n .
If the i n v e r s i o n i s s t i l l m o r e i n c r e a s e d we can f u l f i l the l a s e r condition
(We l e a v e it to the r e a d e r to c h e c k i t s e q u i v a l e n c e with (2. 2)). We now

d i s c u s s the p e r f o r m a n c e of the l a s e r s o m e w h a t above t h r e s h o l d
where
—
•y SU0n - к. > 0
Again we will u s e the analogy with the p a r t i c l e in the p o t e n t i a l well of
F i g . 23. Note that V(b) d e p e n d s only on the a b s o l u t e value of b. T h u s if
we plot V o v e r the c o m p l e x b - p l a n e , V( | b | ) i s s y m m e t r i c a r o u n d the
V - a x i s . We now d e c o m p o s e the p u s h e s e x e r t e d by F t (t) on the p a r t i c l e
into t h o s e in r a d i a l and t h o s e in t a n g e n t i a l d i r e c t i o n . A f t e r an e x c i t a t i o n
in r a d i a l d i r e c t i o n , the p a r t i c l e f a l l s down to i t s e q u i l i b r i u m value | b | = :
Due to t h e s e p u s h e s , f l u c t u a t i o n s p(t) a r e s u p e r i m p o s e d on r . We t h u s
obtain
b| = ( r q + p(t))
On the o t h e r h a n d , t h e r e i s no r e s t o r i n g f o r c e f o r p u s h e s in t a n g e n t i a l
d i r e c t i o n . Thus the p h a s e p (t) in
undergoes a diffusion p r o c e s s . In c o n c l u s i o n , we thus find the following

form
b+ = ( - — 1
stable ' amplitude phase

amplitude fluctuations fluctuations
We now i n t e r p r e t and extend in an obvious way o u r r e s u l t s in the l a n g u a g e of

m o d e a m p l i t u d e s . Above t h r e s h o l d the l a s e r m o d e a m p l i t u d e i s s t a b l e with
IAEA-SMR-12/32, 35 309
s m a l l s u p e r i m p o s e d f l u c t u a t i o n s . The r e l a x a t i o n t i m e of t h e s e a m p l i t u d e
f l u c t u a t i o n s d e c r e a s e s ( " s t e e p e r p o t e n t i a l w e l l " ) . The p h a s e f l u c t u a t i o n s
of t h e field m o d e a r e now the m a i n s o u r c e of the o p t i c a l line width, which
d e c r e a s e s f u r t h e r with i n c r e a s i n g i n v e r s i o n S 0 .
Our above m o d e l allowed p r e d i c t i o n s in p a r t i c u l a r on the i n t e n s i t y
(or photon) c o r r e l a t i o n f u n c t i o n , which is d e f i n e d by
К =<n2> - < n >2
w h e r e t h e b r a c k e t s denote the s t a t i s t i c a l a v e r a g e and n i s the photon n u m b e r .

If one p l o t s K / ^ n У a s a f u n c t i o n of the output i n t e n s i t y , one e x p e c t s the
b e h a v i o u r i l l u s t r a t e d in F i g . 24.
Our above c o n s i d e r a t i o n s d e m o n s t r a t e c l e a r l y t h e b a s i c d i f f e r e n c e
between " l i g h t f r o m t h e r m a l s o u r c e s " ( l a s e r below t h r e s h o l d ) and l a s e r
light (above t h r e s h o l d ) .
O u r c o r r e s p o n d i n g p r e d i c t i o n s (Haken (1964)) m a d e in the f r a m e w o r k
of a m i c r o s c o p i c t h e o r y have been fully s u b s t a n t i a t e d in e x p e r i m e n t s by
A r m s t r o n g and S m i t h (1965) and m a n y o t h e r s . ( F o r d e t a i l e d r e f e r e n c e s
c o n s u l t Haken (1970), o r t h e S u m m e r School r e p o r t s . ) The t h r e s h o l d r e g i o n ,
which i s not c o v e r e d by o u r above t r e a t m e n t , can be m o s t elegantly t r e a t e d
by the m e t h o d of the F o k k e r - P l a n c k equation (Risken 1965), belonging to
o u r L a n g e v i n equation of the l a s e r . H e r e one c a l c u l a t e s the p r o b a b i l i t y f(b)
J<_
<n>
TRESHOLD
REGION
FIG. 24. K/6i> a s a f u n c t i o n of t h e p h o t o n n u m b e r < n > .
flbl
FIG.25. Q u a l i t a t i v e b e h a v i o u r of f (I b | ) (solid l i n e ) b e l o w t h r e s h o l d . Dashed line: V(|b|).

3 1 0 HAKEN
to find the a m p l i t u d e b. Looking at F i g . 23, it i s r a t h e r s i m p l e to g u e s s

the q u a l i t a t i v e b e h a v i o u r of f(b). F o r s m a l l i n v e r s i o n , the " p a r t i c l e " m a y
be found with t h e g r e a t e s t p r o b a b i l i t y at the bottom of the p o t e n t i a l w e l l .
We thus e x p e c t F i g . 25.
In c o m p l e t e analogy we e x p e c t F i g . 26 f o r t h e r e g i o n above t h r e s h o l d .
One m a y even g u e s s the m a t h e m a t i c a l f o r m of f ( | b | )
f ( I b I ) = N ea'b'2 " ß'b'4
which f o r a < 0 y i e l d s F i g . 24 and f o r a > 0 F i g . 25 (N i s a n o r m a l i z a t i o n

f a c t o r ) . A m a z i n g l v enough, it t u r n s out that f < | b | ) m a y be d i r e c t l y e x p r e s s e d
by the p o t e n t i a l V( | b | ) in the f o r m :
f ( I b I ) = N exp { - V ( I b I ) / Q }
w h e r e Q m e a s u r e s the s t r e n g t h of the f l u c t u a t i n g f o r c e s F t o t (t).

T h i s d i s t r i b u t i o n f u n c t i o n , f i r s t d e r i v e d by R i s k e n (1965), h a s s i n c e
been checked in m a n y e x p e r i m e n t s ( A r m s t r o n g and S m i t h , A r e c c h i et a l . ,
and m a n y o t h e r s ) .
FIG.26. Q u a l i t a t i v e b e h a v i o u r of f ( | b | ) (solid l i n e ) a b o v e t h r e s h o l d . Dashed line: V(|b|).
2.2. Analogy with p h a s e t r a n s i t i o n s
P h a s e t r a n s i t i o n s (in t h e i r t h e r m o d y n a m i c s e n s e ) a r e w e l l known f o r
s y s t e m s in t h e r m a l e q u i l i b r i u m . E x a m p l e s a r e the f e r r o m a g n e t i c t r a n s i t i o n ,
t h e l i q u i d - g a s t r a n s i t i o n , and the s u p e r c o n d u c t i n g t r a n s i t i o n . B e c a u s e the
l a s e r i s — in c o n t r a s t to t h e s e s y s t e m s — a s y s t e m f a r f r o m t h e r m a l
e q u i l i b r i u m , it c a m e a s a s u r p r i s e to m a n y p h y s i c i s t s t h a t the l a s e r
t h r e s h o l d m a y be u n d e r s t o o d a s s e c o n d - o r d e r p h a s e t r a n s i t i o n .
In t h e f o l l o w i n g we i n d i c a t e s o m e of the m o s t i m p o r t a n t f e a t u r e s without
going into the d e t a i l s . Some a n a l o g i e s of a q u a l i t a t i v e n a t u r e a r e exhibited
in F i g . 27.
B e c a u s e the field i s coupled to the a t o m i c p o l a r i z a t i o n ( c o m p a r e
Eq. (12) of T a b l e I) a p h a s e t r a n s i t i o n of the light field i s c o n n e c t e d with
that of the l a s e r a t o m s . With r e s p e c t to the a t o m s it i s indeed p o s s i b l e
to d i s c u s s the p h a s e t r a n s i t i o n in the t h e r m o d y n a m i c l i m i t N oo, f o r N / V
f i n i t e (N n u m b e r of a t o m s ) . In the c a s e of the s i n g l e - m o d e l a s e r , the
l a s e r t h r e s h o l d m a y be i n t e r p r e t e d by the Landau t h e o r y of p h a s e t r a n s i t i o n s .
IAEA-SMR-12/32, 35 3 1 1
FERROMAGNET LASER
DISORDERED
Î \ i
PHASE
1
т ф 4I/ÎP -4/1P '
RANDOM SPIN RANDOM PHASES
ORIENTATION
ORDERED PHASE
ONE SINGLE PHASE
BROKEN SYMMETRY IN SPACE IN TIME

(ORIENTATION) (SINGLE PHASE)
SYMMETRY
RESTORING SPIN WAVES PHASE FLUCTUATION
EFFECTS (PHASE DIFFUSION)
FIG.27. Q u a l i t a t i v e a n a l o g i e s b e t w e e n f e r r o m a g n e t and l a s e r .
FIG. 28. Q u a l i t a t i v e d e p e n d e n c e of l a s e r p o w e r o u t p u t on p o w e r i n p u t .
312 HAKEN
F o r t h i s p u r p o s e we e s t a b l i s h t h e following c o r r e s p o n d e n c e :
F e r r o m a g n e t in the m e a n - f i e l d Single m o d e l a s e r
theory
distribution function
f = N exp ( - F / k T ) f = N exp ( - B / Q )
N : normalization factor
F : f r e e energy B: " p o t e n t i a l "

F = a(T) I M| 2
+ /3(Т)|м| В = a(d)|b|2 +ß|b|4
M: m e a n field b: field a m p l i t u d e
or(T) = a ( T - T c ) «(d) = a ( d c - d )
pump p a r a m e t e r
temperature (atomic inversion)
critical inversion
critical temperature
order parameter
M < • b
9F ЭВ
entropy S = - —
Öd
S = Sn disordered phase So
ordered phase = s0 + (dc-d)

=So+2ß (T
-Tc) 2ß
continuous transition
specific heat efficiency
' T9S0/ST disordered phase

as,
ad
:
С
C = dd —
T(9S/3T)= Tas 0 /aT ordered phase 9d
^ H
• a2Tc 3d " 23-
2ß
As i s shown in t h e above s c h e m e , the e f f i c i e n c y i s t h e analogue of the

s p e c i f i c h e a t . B e c a u s e S(i?) i s c o n t i n u o u s , but C(C) i s d i s c o n t i n u o u s , t h e
l a s e r shows a s e c o n d - o r d e r p h a s e t r a n s i t i o n . (Note t h a t the e f f i c i e n c y i s t h e
s l o p e of the c u r v e s in F i g . 28). It should be noted t h a t in p r a c t i c a l c a s e s
t h e s l o p e u s u a l l y s h o w s no s h a r p d i s c o n t i n u i t y . T h i s p h e n o m e n o n i s well
known f r o m p h a s e t r a n s i t i o n s of c o n v e n t i o n a l s y s t e m s in r e s t r i c t e d
IAEA-SMR-12/32, 35 3 1 3
g e o m e t r i e s . On the o t h e r hand it h a s been shown by V. D o h m , t h a t in t h e

l a s e r t h e r e e x i s t s a w e l l - d e f i n e d " t h e r m o d y n a m i c l i m i t " , so t h a t t h e
n o t a t i o n of t h e " s e c o n d - o r d e r p h a s e - t r a n s i t i o n of t h e l a s e r " i s c o m p l e t e l y
justified.
We f i n a l l y p r e s e n t a s t r i k i n g a n a l o g y b e t w e e n l a s e r with a c o n t i n u u m
of m o d e s and a o n e - d i m e n s i o n a l s u p e r c o n d u c t o r .
D i s t r i b u t i o n of t h e e l e c t r i c f i e l d E (x) ( G r a h a m and H a k e n )
f =exp(-^ J j a Е 2 (Х) + Ь Е 4 ( Х ) + | ( i i L - k 0 ) E | 2 | d v J
where
S u p e r c o n d u c t o r : p a i r - w a v e f u n c t i o n Ф(х)
D i s t r i b u t i o n f u n c t i o n of t h e G i n z b u r g - L a n d a u t h e o r y :
f =e x
p(-pj f { a ' H 2 © + b ' H 4 ( x ) + j (i V - dvj
at T = T c : a 1 c h a n g e s s i g n !
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B i o l o g y , V e r s a i l l e s 1 9 6 9 , (MAROIS, M . , E d . ) C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e , Paris ( 1 9 7 1 ) .
K U R N I T , N . A . , ABELLA, I . D . , H A R T M A N N , R . S . , Phys. R e v . L e t t . (1964) 5 6 7 .

3 1 4 HAKEN
LAMB, W . E . , J r . , P h y s . R e v . 134 (1964) 1 4 2 9 .
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(CHRETIEN, M . , GROSS, E . P . , DESER, S . , Eds) G o r d o n and B r e a c h ( 1 9 6 8 ) .
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C o h e r e n t L i g h t , (MILES, P . A . , E d . ) , A c a d e m i c Press ( 1 9 6 4 ) . (b) C o u r s e XLII, 1969, Q u a n t u m O p t i c s
(GLAUBER, R . , E d . ) , A c a d e m i c Press ( 1 9 6 9 ) .
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1AEA-SMR-12/31,32
LASERS: EXPERIMENTAL AND APPLICATIONS
D . J . BRADLEY
Department of Pure and Applied Physics,
The Queen's University of Belfast,
Northern Ireland, United Kingdom
Abstract
LASERS: EXPERIMENTAL AND A P P L I C A T I O N S .

1 . Laser a n d m e a s u r e m e n t t e c h n i q u e s ; 1 . 1 . O r g a n i c d y e lasers: f r e q u e n c y n a r r o w i n g a n d t u n i n g ,
1 . 2 . Pulsed d y e l a s e r s , 1 . 3 . C o n t i n u o u s - w o r k i n g d y e lasers, 1 . 4 . G e n e r a t i o n a n d m e a s u r e m e n t of u l t r a - s h o r t
p u l s e s , 1 . 5 . M e a s u r e m e n t of p i c o s e c o n d p u l s e d u r a t i o n s , 1 . 6 . F r e q u e n c y - t u n a b l e m o d e - l o c k e d d y e l a s e r s ,
1 . 7 . D i r e c t p h o t o e l e c t r i c m e a s u r e m e n t s of p i c o s e c o n d pulses, 1 . 8 . E l e c t r o n - o p t i c a l c h r o n o g r a p h y ,
1 . 9 . D e t e c t i o n of s a t e l l i t e p u l s e s a n d s u b - s t r u c t u r e f r o m s t i e a k - c a m e r a m e a s u r e m e n t s , 1.10. Measurement
of C . W . m o d e - l o c k e d d y e l a s e r s ; 2 . S e l e c t i v e e x c i t a t i o n s p e c t r o s c o p y , 2 . 1 . S e l e c t i v e e x c i t a t i o n of
r u b i d i u m , 2 . 2 . S t i m u l a t e d S t o k e s and a n t i - S t o k e s e l e c t r o n i c R a m a n s c a t t e r i n g , 2 . 3 . Ba I s p e c t r a .
GENERAL INTRODUCTION
It would be. i m p o s s i b l e t o a d e q u a t e l y c o v e r in s e v e n l e c t u r e s t h e r e c e n t
d e v e l o p m e n t s in l a s e r s w h i c h a r e l i k e l y to be i m p o r t a n t f o r t h e s t u d y of
a t o m s and m o l e c u l e s , l e t a l o n e t h e m a n y e x c i t i n g p o s s i b i l i t i e s now a p p a r e n t
in l a s e r p h y s i c s . T h e s e i n c l u d e l a s e r f u s i o n and c o m p r e s s i o n ; p l a s m a
g e n e r a t i o n , h e a t i n g and d i a g n o s i s ; l a b o r a t o r y a s t r o p h y s i c s ; e l e c t r o n - p h o t o n
and p h o t o n - p h o t o n i n t e r a c t i o n s ; b i o p h y s i c s , o p t o - e l e c t r o n i c s and i n f o r m a t i o n
p r o c e s s i n g . F o r a t o m i c and m o l e c u l a r p h y s i c s , of m o s t s i g n i f i c a n c e i s t h e
p r e s e n t a v a i l a b i l i t y of t u n a b l e l a s e r s o u r c e s c o v e r i n g t h e u l t r a v i o l e t ,
v i s i b l e and i n f r a r e d s p e c t r a l r e g i o n s , with a wide r a n g e of p o w e r s , and
with d u r a t i o n s v a r i a b l e f r o m c o n t i n u o u s w o r k i n g to a s s h o r t a s one p i c o -
s e c o n d . H e r e t h e p r o p e r t i e s of f r e q u e n c y n a r r o w e d and t u n e d d y e l a s e r s ,
w h i c h a r e p l a y i n g an i n c r e a s i n g l y i m p o r t a n t r o l e in a t o m i c s p e c t r o s c o p y ,
w i l l be d e s c r i b e d f i r s t , f o l l o w e d by a d i s c u s s i o n of t h e g e n e r a t i o n and
m e a s u r e m e n t of u l t r a - s h o r t p u l s e s , w h i c h now p e r m i t t h e i n v e s t i g a t i o n of
p i c o s e c o n d m o l e c u l a r r e l a x a t i o n t i m e s . A s e x a m p l e s of t h e a p p l i c a t i o n s
of t h e s e new l a s e r s o u r c e s , s e l e c t i v e e x c i t a t i o n and s c a t t e r i n g , and e x c i t e d
s t a t e a b s o r p t i o n of a t o m s and m o l e c u l e s w i l l be d e s c r i b e d . F i n a l l y , t h e
m o s t r e c e n t d e v e l o p m e n t s in m o l e c u l a r and q u a s i - m o l e c u l a r l a s e r s in t h e
v a c u u m u l t r a v i o l e t w i l l be r e v i e w e d . W h i l e a d v a n c e s in a l l t h e s e f i e l d s
h a v e b e e n m a d e p o s s i b l e by r e s e a r c h e s c a r r i e d out in s e v e r a l l a b o r a t o r i e s ,
f o r c o n v e n i e n c e t h e p r e s e n t s t a t e of t h e a r t w i l l be i l l u s t r a t e d , w h e r e
p o s s i b l e , by r e s u l t s o b t a i n e d in o u r l a b o r a t o r i e s at B e l f a s t and t h e n
r e f e r e n c e only w i l l be m a d e to t h e w o r k of o t h e r r e s e a r c h g r o u p s . A g a i n
b e c a u s e of t h e l i m i t a t i o n s of t i m e , t h e e x a m p l e s c h o s e n w i l l n e c e s s a r i l y
h a v e to be highly s e l e c t i v e .
3 1 5
WAVE LENGTH (A) —
2000 3000 4000 5000 6000 7000 9000 10000 11000 12000
I
DYE
TYPE 0XA20LES / \ XANTHENES CYAN I NES
COUMARINS
FIG. 1. Wavelength ranges of a v a i l a b l e dye lasers.

I A E A - S M R - 1 2 / 3 1 , 32 3 17
Hj
XANTHENE
} C£0 4
CRESYL VIOLET PERCHLORATE
FIG.2. T y p i c a l o r g a n i c dye m o l e c u l a r s t r u c t u r e s .
1. L A S E R AND M E A S U R E M E N T T E C H N I Q U E S
1. 1. O r g a n i c dye l a s e r s : f r e q u e n c y n a r r o w i n g and t u n i n g
W h i l e c a p a b l e of p r o d u c i n g h i g h p o w e r s , the o r i g i n a l r u b y and
n e o d y m i u m s o l i d - s t a t e l a s e r s s u f f e r e d f r o m the s e r i o u s d e f e c t of f i x e d
f r e q u e n c i e s . T h e e m i s s i o n s p e c t r a of f l u o r e s c e n t o r g a n i c d y e s a r e
b r o a d and t h e r e i s a l a r g e n u m b e r of d y e s with f l u o r e s c e n c e c o v e r i n g t h e
o p t i c a l s p e c t r u m f r o m 340 to 1170 m m ( F i g . 1). O r g a n i c d y e s a r e
c o m p l i c a t e d m o l e c u l e s c o n t a i n i n g m a n y a t o m s a r r a n g e d in p l a n a r s t r u c t u r e s
with î r - e l e c t r o n bonding ( F i g . 2). T h e p e a k a b s o r p t i o n c r o s s - s e c t i o n i s of
t h e o r d e r of t h e e x t e n s i o n of t h e 7r-electron cloud and the e l e c t r o n i c e n e r g y
l e v e l s a r e c o n s i d e r a b l y b r o a d e n e d by v i b r a t i o n a l and r o t a t i o n a l o s c i l l a t i o n s .
318 BRADLEY
Singlet states Triplet states
CONFIGURATION COORDINATE
FIG. 3. Organic dye e l e c t r o n i c m o l e c u l a r energy levels and transitions.
The m o l e c u l a r e n e r g y l e v e l s a r e shown in ( F i g . 3). B e c a u s e of the v e r y

f a s t r a d i a t i o n l e s s i n t e r n a l c o n v e r s i o n t r a n s i t i o n s within t h e m a n i f o l d of
e x c i t e d s i n g l e t s t a t e s , the l a s i n g t r a n s i t i o n s o c c u r f r o m t h e bottom
v i b r a t i o n a l l e v e l of the f i r s t excited e l e c t r o n i c s t a t e , Sj, to the ground s t a t e ,
S 0 , h i g h e r v i b r a t i o n a l l e v e l s and the r e s u l t i n g b r o a d band (~1000 cm" 1 )
f l u o r e s c e n c e e m i s s i o n i s h o m o g e n e o u s l y b r o a d e n e d . B e c a u s e of r a p i d
t h e r m a l i z a t i o n in both t h e e x c i t e d and ground e l e c t r o n i c s t a t e s the dye
l a s e r o p e r a t e s a s a f o u r - l e v e l s y s t e m but e l e c t r o n i c s i n g l e t - t o - t r i p l e t
i n t e r - s y s t e m c r o s s i n g c a n l e a d to t r i p l e t s t a t e a b s o r p t i o n l o s s e s , which c a n
s e r i o u s l y a f f e c t l a s i n g action s i n c e the t r i p l e t a b s o r p t i o n band m a y o v e r l a p
the f l u o r e s c e n c e band. A l s o the s h o r t f l u o r e s c e n c e l i f e t i m e s , t y p i c a l l y
I A E A - S M R - 1 2 / 3 2 , 35 319
of a few n a n o s e c o n d s , s e v e r e l y r e s t r i c t t h e s t o r a g e of e n e r g y in t h e a c t i v e
m e d i a and dye l a s e r s m u s t be c o n s i d e r e d a s q u a s i - c o n t i n u o u s - w o r k i n g
d e v i c e s , even when p u m p e d by f a s t r i s i n g f l a s h l a m p s , o r o t h e r l a s e r p u l s e s .
A f t e r o p t i c a l p u m p i n g new c h e m i c a l s p e c i e s , t r a n s i e n t o r p e r m a n e n t , m a y
be c r e a t e d and t h e s e p r o d u c t s c a n play an i m p o r t a n t r o l e in dye l a s e r s .
T h e s t r u c t u r e and w a v e l e n g t h s of t h e a b s o r p t i o n and e m i s s i o n s p e c t r a a l s o
depend on t h e s o l v e n t e m p l o y e d . W a v e l e n g t h c h a n g e s a r e u s u a l l y r e l a t e d
to t h e s o l v e n t d i e l e c t r i c c o n s t a n t and to the index of r e f r a c t i o n . R a d i a t i v e
l i f e t i m e s and f l u o r e s c e n c e q u a n t u m e f f i c i e n c y a r e a l s o s o l v e n t - d e p e n d e n t .
T h u s the f l u o r e s c e n c e e f f i c i e n c y of a dye s u c h a s p y r o n i n Y [1] i n c r e a s e s
f r o m 40% in m e t h a n o l to n e a r l y 100% in g l y c e r o l b e c a u s e of d a m p i n g of
t h e t o r s i o n a l v i b r a t i o n s . By adding s a t u r a t e d h y d r o c a r b o n b r i d g e s to s t i f f e n
t h e m o l e c u l a r s t r u c t u r e D r e x h a g e h a s d e s i g n e d a new dye pyronin 105,
with a f l u o r e s c e n t q u a n t u m yield of 100% in e t h a n o l [ 1 ] . The p H - v a l u e of
the solution i s a l s o i m p o r t a n t s i n c e a p r o t o n added to an e x c i t e d m o l e c u l e
g i v e s l a s i n g a c t i o n o v e r a d i f f e r e n t s p e c t r a l r e g i o n [2] and t h u s e f f e c t i v e l y
i n c r e a s e s t h e tuning r a n g e a v a i l a b l e f r o m a s i n g l e d y e . S i m i l a r l y the
f o r m a t i o n of e x c i p l e x e s , which a r e i n t r i n s i c a l l y u n s t a b l e in t h e ground s t a t e
and have the a b s o r p t i o n and e m i s s i o n bands widely s e p a r a t e d , gives a
w i d e r tuning r a n g e .
1.2. P u l s e d dye l a s e r s y s t e m s
Sorokin [3] and S c h ä f e r [4] and t h e i r c o l l a b o r a t o r s f i r s t a c h i e v e d n e a r

i n f r a r e d l a s e r action in p o l y m e t h i n e and p h t h a l o c y a n i n e d y e s pumped by
g i a n t - p u l s e ruby l a s e r s . S e c o n d - h a r m o n i c g e n e r a t i o n of ruby and n e o d y m i u m
l a s e r p u l s e s p e r m i t the p u m p i n g of the c o u m a r i n and x a n t h e n e d y e s l a s i n g
in the v i s i b l e and n e a r u l t r a v i o l e t . T h e p u l s e d n i t r o g e n l a s e r pump e x t e n d e d
the s p e c t r a l r a n g e into the u l t r a v i o l e t , e m p l o y i n g s c i n t i l l a t o r d y e s [5] .
E f f e c t i v e f r e q u e n c y n a r r o w i n g w a s f i r s t d e m o n s t r a t e d in a l a s e r p u m p e d
s y s t e m by S o f f e r and M c F a r l a n d [6] , who r e p l a c e d one of the l a s e r
cavity m i r r o r s with a d i f f r a c t i o n g r a t i n g u s e d in a u t o - c o l l i m a t i o n . By
adding an i n t r a c a v i t y F a b r y - P e r o t e t a l o n and p u m p i n g longitudinally s i n g l e
m o d e o p e r a t i o n [7, 8] with a band width of < 10" 3 n m w a s a c h i e v e d . S e v e r a l
o t h e r f i n e - t u n i n g a r r a n g e m e n t s have s i n c e been e m p l o y e d including p r i s m s ,
L y o t - f i l t e r s and F a r a d a y - r e s o n a t o r s , a l l b a s e d on the i n s e r t i o n of a d i s p e r s i v e
e l e m e n t into the dye l a s e r c a v i t y . P r i s m s and F a b r y - P e r o t é t a l o n s , u s e d
s i n g l y , o r m u l t i p l y , have p r o v e d to be m o s t c o n v e n i e n t and e f f e c t i v e and
a r e l e s s e a s i l y d a m a g e d . Single t r a n s v e r s e , s i n g l e l o n g i t u d i n a l m o d e
o p e r a t i o n [9] (bandwidth < 3 5 MHz) w a s obtained by the f u r t h e r i n s e r t i o n of
an a p e r t u r e in the l a s e r c a v i t y , f r e q u e n c y tuned by the c o m b i n a t i o n of an
e c h e l l e g r a t i n g and t i l t e d F a b r y - P e r o t i n t e r f e r o m e t e r ( F i g . 4). The output
s p e c t r a l bandwidth of 34 MHz of t h i s dye l a s e r ( F i g . 5) i s in good a g r e e m e n t
with t h e F o u r i e r t r a n s f o r m width of t h e 2 0 - n s h a l f - w i d t h l a s e r p u l s e . O v e r
a p e r i o d of 60 h o u r s t h e abdolute f r e q u e n c y d r i f t e d to l o n g e r w a v e l e n g t h s by
only 5 x 10" 2 cm" 1 , showing t h e o v e r a l l e x c e l l e n t s t a b i l i t y of t h e l a s e r .
The output coupling b e a m - s p l i t t e r and the dye c e l l windows w e r e wedged
to avoid s u b c a v i t i e s .
B e c a u s e of the g r e a t e r n u m b e r of cavity t r a n s i t s , f r e q u e n c y n a r r o w i n g
i s m o r e e a s i l y obtained with the l o n g e r d u r a t i o n f l a s h l a m p p u m p e d dye
l a s e r s . Since F a b r y - P e r o t i n t e r f e r o m e t e r s have a n g u l a r d i s p e r s i o n s g r e a t l y
s u p e r i o r to t h o s e of g r a t i n g s o r p r i s m s [11] f r e q u e n c y s e l e c t i o n i s l e s s
3 2 0 BRADLEY
FABRY- DYE APERTURE ECHELLE

PEROT CELL GRATING
PRISM
REFLECTOR
ELEVATION
PLAN
FIG.4. S i n g l e - t r a n s v e r s e , s i n g l e - l o n g i t u d i n a l m o d p d y e l a s e r t u n e d by e c h e l l e g r a t i n g and F a b r y - P e r o t
etalon. P o l y m e t h i n e d y e p u m p e d by 100 MW • c r n ! ruby g i a n t pulse of 40 ns d u r a t i o n .
FIG. 5 . S p e c t r a l b a n d w i d t h of l a s e r of F i g . 4 m e a s u r e d w i t h a d e f o c u s s e d s p h e r i c a l F - P i n t e r f e r o m e t e r [10] of
375 MHz free spectral r a n g e . D y e l a s e r 20 ns pulse of 150 kW- c m " 2 .
I A E A - S M R - 1 2 / 3 2 , 35 3 2 1
FIG, 6 . D e s i g n of o p t i c a l l y c o n t a c t e d , narrow g a p (5 Mm - 500 :.im), F - P i n t e r f e r o m e t e r f i l t e r s used for d y e l a s e r

frequency narrowing and tuning.
mJ ,10 '
-2-5 x 10 '
240 -
200 -
160 -
/2x10"
120 -
80 -
AO -
0. _1_
560 570 580 590 600 610 Л ( n m )
FIG. 7 . T u n i n g e f f i c i e n c y c u r v e s for d i f f e r e n t c o n c e n t r a t i o n s of R h o d a m i n e 6G t u n e d w i t h a 7 | i m g a p
interferometer. Figures d e n o t e t h e m o l a r c o n c e n t r a t i o n s of the d y e s o l u t i o n s in e t h a n o l .
s e n s i t i v e to i n c r e a s e d b e a m d i v e r g e n c e , a r i s i n g f r o m t h e r m a l g r a d i e n t s
in a f l a s h l a m p - p u m p e d d y e . An additional a d v a n t a g e i s the m o d e - s e l e c t i o n
p r o p e r t y of a t i l t e d F a b r y - P e r o t e t a l o n in a l a s e r c a v i t y . P u r e i n t e r f e r o -
m e t r i c tuning of both l o w - e n e r g y [ 12] and h i g h - e n e r g y [ 1 3 ] dye l a s e r s i s t h e
s i m p l e s t m e t h o d of s e l e c t i n g a p a r t i c u l a r band width f r o m the output s p e c t r u m .
The a v a i l a b i l i t y of n a r r o w gap (—6 f j m ) otpically c o n t a c t e d , p e r m a n e n t l y
a d j u s t e d , h i g h - f i n e s s e F a b r y - P e r o t é t a l o n s ( o r i g i n a l l y developed [ 1 4 , 1 5 ]
f o r h i g h - r e s o l u t i o n u. v. s p e c t r o s c o p y f r o m sounding r o c k e t s ) m a k e s e a s y
h i g h - e f f i c i e n c y tuning and n a r r o w i n g . F i g u r e 6 s h o w s the m e t h o d of
c o n s t r u c t i o n of t h e n a r r o w - g a p q u a r t z é t a l o n s . When i n s e r t e d i n s i d e t h e
cavity of a h i g h - e f f i c i e n c y f l a s h l a m p - p u m p e d dye l a s e r , a single um
gap i n t e r f e r o m e t e r with 3 - l a y e r d i e l e c t r i c c o a t i n g s of r e f l e c t i v i t y 65%
r e d u c e s the l a s e r band width to < 0 . 3 n m , with n e g l i g i b l e r e d u c t i o n in t h e
output e n e r g y a s can be s e e n f r o m t h e tuning e f f i c i e n c y c u r v e s of F i g u r e 7.
3 2 2 BRADLEY
FIG. 8. T u n i n g r a n g e of R h o d a m i n e 6G l a s e r o b t a i n e d using a s i n g l e 4 | i m g a p F - P e t a l o n a n d t u n i n g t h r o u g h
o n e f r e e s p e c t r a l r a n g e by r o t a t i o n . T h e r a n g e shown (579 n m t o 6 1 8 n m ) c o u l d b e s h i f t e d t o l o n g e r or
s h o r t e r w a v e l e n g t h s by a l t e r a t i o n of t h e d y e c o n c e n t r a t i o n .
A tuning r a n g e of 40 nm can be c o v e r e d by r o t a t i n g a 4-Mm-gap e t a l o n

( F i g . 8). T h e r a n g e c o v e r e d by an e t a l o n c a n a l s o be changed by v a r i a t i o n
of the dye c o n c e n t r a t i o n s i n c e t h i s a l t e r s the p o s i t i o n of the l a s i n g band width.
T h e s p e c t r a l n a r r o w i n g i s m u c h b e t t e r than the p a s s i v e band width of the
i n t e r f e r o m e t e r . The e t a l o n i s , of c o u r s e , m u l t i p l e p a s s e d i n s i d e the l a s e r
cavity and the r e s u l t a n t l a s e r band width i s c o n s i d e r a b l y n a r r o w e r than
that of the l o w - f i n e s s e i n t e r f e r o m e t e r . The é t a l o n s a r e p e r m a n e n t l y in
a d j u s t m e n t to a p a r a l l e l i s m of > X / 4 0 o v e r the ~ 1 c m a p e r t u r e . Since
only low r e f l e c t i v i t y m u l t i l a y e r s t a c k s a r e e m p l o y e d it i s p o s s i b l e to c o v e r
a s p e c t r a l r a n g e of ~ 2 0 0 nm with one e t a l o n , e. g. both c o u m a r i n d y e s ,
o p e r a t i n g in the blue ( ~ 4 5 0 nm) to R h o d a m i n e В which l a s e s ~ 6 4 0 n m .
F i g u r e 9 s h o w s how f u r t h e r s p e c t r a l n a r r o w i n g can be a c h i e v e d by e m p l o y i n g
a s e c o n d (100 ßm gap) i n t e r f e r o m e t e r in the l a s e r c a v i t y . At the s h o r t e r
w a v e l e n g t h s the tuning r a n g e i s ~ 1 4 0 nm b e c a u s e of the r e d u c e d f r e e
s p e c t r a l r a n g e of t h e i n t e r f e r o m e t e r and the l a s e r line width i s c o r r e s p o n d -
ingly r e d u c e d to 0.15 n m . With 7 - д т and 1 0 0 - м т i n t e r f e r o m e t e r s the
l a s e r line width w a s n a r r o w e d to 0.01 n m , and by r o t a t i n g the 100 ß m
e t a l o n t h i s n a r r o w e d line could be tuned t h r o u g h the 1 . 8 - n m f r e e s p e c t r a l
r a n g e of the 1 0 0 - м т e t a l o n .
T h e s e r e s u l t s d e m o n s t r a t e the e f f i c i e n c y and e a s e with which high
e n e r g y , f l a s h l a m p - p u m p e d dye l a s e r s can be f r e q u e n c y - n a r r o w e d and
tuned with F a b r y - P e r o t i n t e r f e r o m e t e r s . M o r e r e c e n t l y [16] in o u r
l a b o r a t o r i e s a f l a s h l a m p - p u m p e d dye l a s e r h a s been f r e q u e n c y - n a r r o w e d
to 4 MHz and o p e r a t e d in a s i n g l e t r a n s v e r s e and s i n g l e l o n g i t u d i n a l m o d e .
3 17
IAEA-SMR-12/31, 32
— Out pul
< 1 0 MHZ
F. P I F P2 F P.3
7/Ü G A P 500M GAP 5 m m GAP
SINGLE LONGITUDINAL MODE DYE LASER
FIG. 10. O p t i c a l a r r a n g e m e n t for a t u n a b l e , s i n g l e - m o d e f l a s h l a m p p u m p e d d y e l a s e r f r e q u e n c y n a r r o w e d

a n d t u n e d by t h r e e F - P é t a l o n s (5 Mm, 200 u m , 5 m m g a p s ) .
324 BRADLEY
T h e e x p e r i m e n t a l a r r a n g e m e n t i s shown in F i g . 10. A s o a p - a n d - w a t e r
s o l u t i o n of R h o d a m i n e 6G was c i r c u l a t e d t h r o u g h a 5 - c m long, 3 - m m i n t e r n a l
d i a m e t e r dye c e l l . P u m p i n g w a s with a l i n e a r xenon q u a r t z f l a s h l a m p ,
of l e n g t h 5 c m and i n t e r n a l b o r e 2 m m , and an e l e c t r i c a l e n e r g y of up to
20 J in a p o l i s h e d a l u m i n i u m , s i n g l e e l l i p t i c a l r e f l e c t o r a r r a n g e m e n t .
T r a n s v e r s e m o d e s e l e c t i o n i s obtained with a 1.5 m m c i r c u l a r a p e r t u r e
i n s i d e the 50 c m g e n e r a l i z e d c o n f o c a l cavity c o n s i s t i n g of a c o n c a v e 100%
r e f l e c t o r of 3 m r a d i u s of c u r v a t u r e and a 65% r e f l e c t i v i t y plane output
m i r r o r . A m e a s u r e d m o d e d i a m e t e r of 1 m m at t h e plane m i r r o r and
a n e a r - f i e l d p e a k p o w e r d e n s i t y of 2 MW- cm" 2 in a 5 0 0 - n s h a l f - w i d t h l a s e r
p u l s e w a s obtained with an e l e c t r i c a l pumping e n e r g y of 20 J . T h e f i r s t
t i l t e d F a b r y - P e r o t e t a l o n (plate s p a c i n g 5 д т , f i n e s s e 7) n a r r o w e d t h e
l a s e r s p e c t r u m to 0.2 n m and a s e c o n d 200 д т gap e t a l o n f u r t h e r r e d u c e d
t h e band width to 5 x 1 0 " 3 n m . F i n a l l y , a t h i r d e t a l o n of f i n e s s e 20 and
p l a t e s e p a r a t i o n 5 m m s e l e c t e d a single longitudinal m o d e . All the
i n t r a c a v i t y o p t i c a l c o m p o n e n t s w e r e wedged and the t h r e e é t a l o n s w e r e
a n t i - r e f l e c t i o n - c o a t e d on t h e i r e x t e r n a l s u r f a c e s . Single m o d e o p e r a t i o n
p e a k p o w e r d e n s i t y w a s 0.5 MW-cm" 2 in a 4 0 0 - n s h a l f - w i d t h p u l s e . By
k e e p i n g the dye t e m p e r a t u r e c o n s t a n t to ~ 0 . 1 °C at 16°C the o v e r a l l
f r e q u e n c y s t a b i l i t y w a s m a i n t a i n e d to within 12 MHz. A l a s e r line width
of ~ 4 MHz, a s m e a s u r e d with a 20 c m d e f o c u s s e d s p h e r i c a l F a b r y - P e r o t
i n t e r f e r o m e t e r , w a s obtained at a p u m p i n g e n e r g y of 8 J . The p u l s e
h a l f - w i d t h of 100 ns then c o r r e s p o n d e d to the F o u r i e r t r a n s f o r m l i m i t of
4 MHz, showing t h a t the l a s e r w a s o p e r a t i n g without any f r e q u e n c y
c h i r p i n g [17] . T h i s dye l a s e r t h e r e f o r e h a s a f r e q u e n c y p r e c i s i o n s u i t a b l e
f o r h i g h - r e s o l u t i o n a t o m i c s p e c t r o s c o p y . The w e l l d e f i n e d , s i n g l e - t r a n s v e r s é -
m o d e a l s o p e r m i t s the p r e c i s e c a l c u l a t i o n of the l a s e r p o w e r s p a t i a l
distribution.
F r e q u e n c y n a r r o w i n g and tuning h a s a l s o b e e n a c h i e v e d with o t h e r
p u l s e d dye l a s e r s . . H a n s c h [18] h a s a c h i e v e d a l i n e w i d t h of 300 MHz with
a p e a k p o w e r of 4 kW in 5 ns f r o m a R h o d a m i n e l a s e r p u m p e d by a 100 kW,
10 n s , 100 p p s n i t r o g e n l a s e r . N a r r o w i n g and tuning w a s obtained with
an e c h e l l e - g r a t i n g and F a b r y - P e r o t etalon c o m b i n a t i o n , a s f i r s t u s e d f o r
r u b y - p u m p e d dye l a s e r s [ 7 ] . O t h e r tuning e l e m e n t s e m p l o y e d have
i n c l u d e d the Lyot f i l t e r [19], m u l t i p l e p r i s m a r r a n g e m e n t s [ 2 0 , 2 1 ] and
a c o u s t - o p t i c f i l t e r s [ 2 2 ] . T h i s l a s t m e t h o d p e r m i t s a w i d e r tuning r a n g e
of ~ 8 0 n m with R h o d a m i n e d y e s . E l e c t r i c a l tuning can a l s o be a c h i e v e d
with a p i e z o - e l e c t r i c d r i v e n n a r r o w - g a p F a b r y - P e r o t e t a l o n [23]. D i s t r i b -
uted f e e d b a c k t h i c k p h a s e g r a t i n g s have been u s e d to tune s m a l l s o l i d - s t a t e
dye l a s e r s [24] and s p e c t r a l n a r r o w i n g h a s a l s o been obtained by i n j e c t i o n
of the n a r r o w l i n e f r o m an a r g o n ion l a s e r into a n i t r o g e n l a s e r p u m p e d
e x c i p l e x dye l a s e r [25] . F r e q u e n c y l o c k i n g of a f l a s h l a m p - p u m p e d
R h o d a m i n e 6G l a s e r to the D l i n e s of s o d i u m v a p o u r w a s a c c o m p l i s h e d by
e m p l o y i n g a F a r a d a y f i l t e r , u s i n g a s o d i u m v a p o u r c e l l in a s t r o n g
m a g n e t i c field [ 2 6 ] .
T h e h i g h - p e a k p o w e r s and n a r r o w s p e c t r a l band widths obtained f r o m
p u l s e d dye l a s e r s p e r m i t the e f f i c i e n t g e n e r a t i o n of s e c o n d h a r m o n i c
and s u m f r e q u e n c i e s t h u s giving a c o n s i d e r a b l e e x t e n s i o n of the a v a i l a b l e
wavelength range. Tunable second-harmonic generation was f i r s t achieved
by f r e q u e n c y doubling a f l a s h l a m p p u m p e d R h o d a m i n e 6G dye l a s e r output
with a K D P c r y s t a l [27] . A peak p o w e r of 40 W v a r i a b l e f r o m 290 n m to
300 n m w a s o b t a i n e d by tuning t h e dye l a s e r with a d i f f r a c t i o n g r a t i n g .
I A E A - S M R - 1 2 / 3 2 , 35 325
100 7 . MIRROR
) FABRY PEROT
TELESCOPE
530 n m PUMP t ^ j
DYE CELL
40 7. MIRROR
A.D.P. CRYSTAL
TO SPECTROGRAPH
F I G . 11. E x p e r i m e n t a l a r r a n g e m e n t f o r t h e g e n e r a t i o n of m e g a w a t t p o w e r , t u n a b l e s e c o n d h a r m o n i c
f r e q u e n c i e s of R h o d a m i n e 6G d y e l a s e r .
326 BRADLEY
Megawatt p o w e r s t u n a b l e f r o m 280 nm to 290 n m w a s l a t e r obtained with a

dye l a s e r p u m p e d by the s e c o n d h a r m o n i c of a giant p u l s e n e o d y m i u m
l a s e r in the a r r a n g e m e n t [28] shown in F i g . 11. The 4 c m x 1 c m dye c e l l ,
with 5° wedged w i n d o w s , c o n t a i n e d a 3 x 10" 5 M solution of R h o d a m i n e 6G
in e t h a n o l and w a s t r a n s v e r s e l y pumped by t h e s e c o n d h a r m o n i c f r e q u e n c y
( g e n e r a t e d in p h a s e - m a t c h e d ADP) of an a m p l i f i e d Q - s w i t c h e d n e o d y m i u m :
g l a s s l a s e r . T h e o n e - j o u l e , 22 ns p u m p i n g p u l s e w a s f o c u s s e d into t h e
dye c e l l with a 50 c m f o c a l length c y l i n d r i c a l l e n s . The 40 c m dye l a s e r
cavity with a 100% r e f l e c t i v i t y d i r e l e c t r i c m i r r o r and a t w o - p l a t e r e s o n a n t
r e f l e c t o r (~40% r e f l e c t i v i t y ) gave an output of 300 m j in a 22 n s p u l s e ,
with a t o t a l s p e c t r a l width of 8 nm a r o u n d 570 n m . A 7.5 ß m gap F a b r y -
P e r o t e t a l o n r e d u c e d the s p e c t r a l width to 0.5 nm with an output of 240 m j
t u n a b l e o v e r t h e 22 n m e t a l o n f r e e s p e c t r a l r a n g e by r o t a t i o n of t h e
i n t e r f e r o m e t e r . A G a l i l e a n t e l e s c o p e in t h e cavity expanded the b e a m a r e a
to avoid d a m a g i n g the i n t e r f e r o m e t e r d i e l e c t r i c c o a t i n g s . T h e f r e q u e n c y
n a r r o w e d dye l a s e r output g e n e r a t e d s e c o n d h a r m o n i c in a n o t h e r A D P
c r y s t a l p h a s e m a t c h e d , f o r n o r m a l i n c i d e n c e , at 285 n m . T h e r e s u l t i n g
1 MW p u l s e (20 m j in 17 n s ) could be f r e q u e n c y tuned f r o m 280 n m to
290 n m without any l o s s of p o w e r , by r o t a t i n g the tuning i n t e r f e r o m e t e r ,
p r o v i d e d the A D P c r y s t a l w a s tuned to t h e p h a s e - m a t c h e d angle f o r e a c h
f r e q u e n c y . The s e c o n d - h a r m o n i c i n t e n s i t y then r e m a i n e d c o n s t a n t o v e r
the tuning r a n g e ( F i g . 12). T h e b r o a d - b a n d dye l a s e r output p r o d u c e d a
s e c o n d h a r m o n i c band width 0.8 n m but by n a r r o w i n g the f u n d a m e n t a l l a s e r
band width f r o m 8 to 0.5 nm t h e s e c o n d - h a r m o n i c e n e r g y w a s i n c r e a s e d
f r o m 2 m j to 20 m j . The s p e c t r a l band width a t 280 n m w a s then 0.2 n m
and the r e s u l t i n g p o w e r d e n s i t y was 10 MW . cm" 2 .
By r o t a t i n g the F a b r y - P e r o t f i l t e r to one end of i t s a n g u l a r tuning
r a n g e two f r e q u e n c i e s s e p a r a t e d by t h e f r e e s p e c t r a l r a n g e of 22 nm w e r e
g e n e r a t e d . T h r e e u . v . l i n e s w e r e then obtained c o r r e s p o n d i n g to the two
s e c o n d - h a r m o n i c f r e q u e n c i e s and the s u m f r e q u e n c y when the A D P c r y s t a l
w a s r o t a t e d to t h e a p p r o p r i a t e angle f o r p h a s e m a t c h i n g . It i s s o m e w h a t
m o r e c o n v e n i e n t to tune the u. v. f r e q u e n c y by e m p l o y i n g a b r o a d - b a n d
d y e - l a s e r b e a m and r o t a t i n g the s e c o n d - h a r m o n i c c r y s t a l . T h e r e i s
h o w e v e r a l a r g e l o s s in e f f i c i e n c y f r o m the 10% a c h i e v e d with t h e
f r e q u e n c y - n a r r o w e d d y e - l a s e r b e a m . M o r e r e c e n t l y g e n e r a t i o n of t u n a b l e
u . v . r a d i a t i o n in the s p e c t r a l r a n g e 216-234 n m h a s been o b t a i n e d [29] by
s u m m i n g t h e t h r e e f r e q u e n c i e s of the f u n d a m e n t a l - and s e c o n d - h a r m o n i c
n e o d y m i u m p u m p i n g l a s e r and t h e dye l a s e r in a c a l c i t e c r y s t a l . H o w e v e r ,
a u. v. p o w e r of ~ 1 5 kW only w a s obtained with a n e o d y m i u m pumping
p u l s e of 70 MW so t h e c o n v e r s i o n e f f i c i e n c y i s quite low.
T h u s by e m p l o y i n g a v a r i e t y of l a s e r - p u m p e d and f l a s h l a m p - p u m p e d
dye l a s e r s it i s p o s s i b l e to obtain e x t r e m e l y n a r r o w - b a n d p o w e r f u l light
s o u r c e s t h r o u g h o u t t h e s p e c t r a l r e g i o n of 200 n m to 1200 n m . As will be
s e e n l a t e r t h e s e s o u r c e s have many a p p l i c a t i o n s to a t o m i c and m o l e c u l a r
s p e c t r o s c o p y w h e r e a m i n i m u m amount of f r e q u e n c y tunable e n e r g y i s
r e q u i r e d to p r e p a r e a s a m p l e in a s e l e c t i v e l y e x c i t e d s t a t e .
1. 3. C o n t i n u o u s - w o r k i n g dye l a s e r s
P e t e r s o n , T u c c i o and Snavely [30] obtained t h e f i r s t c o n t i n u o u s - w o r k i n g

(CW) o p e r a t i o n f r o m a flowing solution of R h o d a m i n e 6G in w a t e r
containing s o a p as a d e a g g r e g a t i n g a g e n t . A 1 watt a r g o n l a s e r o p e r a t i n g
I A E A - S M R - 1 2 / 3 2 , 35 327
at X 514.5 n m was f o c u s s e d by a 32 m m f o c a l l e n g t h m i c r o s c o p e o b j e c t i v e
t h r o u g h the f l a t s a p p h i r e m i r r o r to a point in t h e dye s o l u t i o n c l o s e to the
i n s i d e s u r f a c e of t h e m i r r o r . T h e g a s l a s e r b e a m d i a m e t e r h e r e w a s
11 м т , c o r r e s p o n d i n g to a p u m p i n g p o w e r of ~ 1 MW • cm" 2 . The input
m i r r o r had a d i e l e c t r i c c o a t i n g of 76% t r a n s m i s s i o n at 5145 A and
r e f l e c t i v i t y 99.5% at the dye l a s e r w a v e l e n g t h . The s p h e r i c a l output m i r r o r
w a s d e n s e flint g l a s s of r a d i u s of c u r v a t u r e 4.55 m m c o a t e d a s the s a p p h i r e
window, with both c o a t i n g s i m m e r s e d in the c i r c u l a t i n g d y e . The output
coupling t r a n s m i s s i o n w a s 0.3% and t h e two m i r r o r s w e r e s p a c e d 0.02 m m
c l o s e r than t h e s e p a r a t i o n f o r p e r f e c t h e m i s p h e r i c a l f o c u s , so as to o b t a i n
a s t a b l e l a s e r cavity c o n f i g u r a t i o n . The 2.5 x 10" 4 M R h o d a m i n e 6G dye
solution in w a t e r with 1.5% T r i t o n X100 w a s c i r c u l a t e d with a t r a n s v e r s e
flow r a t e of 200 c m • s" 1 at t h e f o c u s . Methanol could a l s o be u s e d but the
t h e r m a l e f f e c t s [31] i n c r e a s e d l e a d i n g to i n t e n s i t y v a r i a t i o n s . Oxygen
d i s s o l v e d in the w a t e r o r t h e a l c o h o l q u e n c h e s t h e t r i p l e t s t a t e a b s o r p t i o n
by r e d u c i n g the t r i p l e t s t a t e l i f e t i m e to 10" 7 s . T h e g a s - l a s e r t h r e s h o l d
p o w e r w a s 120 mW f o r m e t h a n o l and 200 m W f o r w a t e r solution and the
d y e - l a s e r output p o w e r w a s 30 m W at 597 n m with a 1 - w a t t p u m p .
L a t e r t h i s o r i g i n a l d e s i g n w a s adapted and a l t e r e d to give g r e a t e r
f l e x i b i l i t y and to p e r m i t the i n s e r t i o n of tuning e l e m e n t s . One cavity d e s i g n ,
which w a s a l s o u s e d to o b t a i n p a s s i v e m o d e - l o c k i n g of the CW dye l a s e r
[32, 33] i s shown in F i g . 13.
A m o r e r a d i c a l change in the d e s i g n of CW dye l a s e r s due to D i e n e s ,
Ippen and Shank [34] e m p l o y e d a B r e w s t e r - a n g l e d dye c e l l w h o s e
a s t i g m a t i s m i s c o m p e n s a t e d f o r by the u s e of a p a i r of o f f - a x i s s p h e r i c a l
FIG.13. CW dye l a s e r c a v i t y p e r m i t t i n g t u n i n g a n d passive m o d e - l o c k i n g .

328 BRADLEY
m i r r o r s . In t h i s a r r a n g e m e n t the dye c e l l i s p u m p e d f r o m both s i d e s

s y m m e t r i c a l l y in t h e a r g o n - i o n - l a s e r s t a n d i n g - w a v e field and the g a s - l a s e r
b e a m e n t e r s t h e dye c e l l d i r e c t l y so f e e d b a c k i s p r e v e n t e d . Since heat i s
g e n e r a t e d u n i f o r m l y i n s i d e the dye c e l l t h e r m a l e f f e c t s a r e l e s s and p y r e x
o r q u a r t z can be u s e d i n s t e a d of s a p p h i r e . The t h e r m a l l y induced l e n s i s
e a s i l y c o m p e n s a t e d f o r by r e a d j u s t i n g the cavity l e n g t h . The dye c e l l w a s
1 m m t h i c k and the w a i s t d i a m e t e r w a s ~ 2 5 ium. The c u r v e d m i r r o r s had
r a d i i of c u r v a t u r e 5 c m o r 10 c m and the angle w a s 6° f o r o p t i c a l
c o m p e n s a t i o n . Using a 3.5 W pumping a r g o n ion l a s e r up to 30% c o n v e r s i o n
h a s been a c h i e v e d (1 watt d y e - l a s e r p o w e r ) with 4 x 10" 4 M R h o d a m i n e 6G
in w a t e r and 4% A m m o n y x L . O. and tuning f r o m 576 nm to 634 n m . T h e
output m i r r o r t r a n s m i s s i o n of 5% was not n e c e s s a r i l y o p t i m u m . This Bell
L a b o r a t o r i e s l a s e r , which showed t h a t both high p o w e r c o n t i n u o u s w o r k i n g
and a wide tuning r a n g e w a s o b t a i n a b l e , a l s o had a s h o r t - t e r m f r e q u e n c y
s t a b i l i t y of b e t t e r t h a n 0.01 n m .
E m p l o y i n g a s i m i l a r cavity s y s t e m G a b e l and H e r c h e r [35] have
g e n e r a t e d d y e - l a s e r s e c o n d - h a r m o n i c f r e q u e n c i e s in an i n t r a c a v i t y l i t h i u m
f o r m a t e c r y s t a l p l a c e d at t h e w a i s t of a p a i r of s p h e r i c a l m i r r o r s . It i s
t h u s p o s s i b l e t o obtain CW tunable f r e q u e n c i e s , c o v e r i n g t h e s a m e s p e c t r a l
r e g i o n s in t h e u. v. and v i s i b l e a s the f u n d a m e n t a l and h a r m o n i c f r e q u e n c i e s
of p u l s e d dye l a s e r s . T h e s e new light s o u r c e s should h a v e an i m m e d i a t e
i m p a c t on a t o m i c and m o l e c u l a r s p e c t r o s c o p y ,
1.4. G e n e r a t i o n and m e a s u r e m e n t of u l t r a - s h o r t p u l s e s
The l a s i n g band w i d t h s of n e o d y m i u m : g l a s s and dye l a s e r s a r e s u f f i c i e n t l y

l a r g e to p e r m i t t h e g e n e r a t i o n of p u l s e s a s s h o r t a s 10" 1 3 s e c o n d s . U l t r a -
s h o r t light p u l s e s w e r e f i r s t obtained in 1965 by M o c k e r and Collins [36]
f r o m a g i a n t - p u l s e ruby l a s e r containing a s a t u r a b l e a b s o r b e r dye. Soon
a f t e r t h i s m o d e - l o c k i n g of the n e o d y m i u m : g l a s s l a s e r w a s a c h i e v e d by
De M a r i a and c o - w o r k e r s [37] . With t h e d e v e l o p m e n t of dye l a s e r s
t u n a b l e - f r e q u e n c y u l t r a - s h o r t p u l s e s b e c a m e a v a i l a b l e by p u m p i n g d y e s
with m o d e - l o c k e d r u b y [38] o r s e c o n d - h a r m o n i c n e o d y m i u m [39] l a s e r
p u l s e t r a i n s . Self m o d e - l o c k i n g of dye l a s e r s by p o l y m e t h i n e s a t u r a b l e
a b s o r b e r s [ 4 0 , 4 1 ] p r o v e d to be the b e s t m e t h o d f o r the g e n e r a t i o n of
picosecond pulses [42,43].
M o d e - l o c k e d n e o d y m i u m : g l a s s l a s e r s a r e c a p a b l e of p r o d u c i n g the
h i g h e s t p o w e r and e n e r g y p e r p u l s e . A t y p i c a l e x p e r i m e n t a l a r r a n g e m e n t
[44] i s shown in F i g . 14 with t h e P o c k e l s c e l l d r i v e n by a l a s e r - t r i g g e r e d
s p a r k gap [45] f o r s w i t c h i n g out a single p u l s e f o r f u r t h e r a m p l i f i c a t i o n
( F i g . 15). In t h i s m a n n e r gigawatt p o w e r s and g r e a t e r c a n be r e a d i l y
obtained in s i n g l e p u l s e s of d u r a t i o n ~ 1 0 p s . In the f i r s t few y e a r s of
s t u d i e s of m o d e - l o c k e d n e o d y m i u m l a s e r s t h e r e w a s c o n s i d e r a b l e c o n f u s i o n
both about t h e n a t u r e of the u l t r a - s h o r t p u l s e g e n e r a t i o n p r o c e s s e s and
the i n t e r p r e t a t i o n of t h e e x p e r i m e n t a l r e s u l t s . B e c a u s e of t h e wide
a p p l i c a t i o n of e r r o n e o u s m e t h o d s of m e a s u r e m e n t of p u l s e d u r a t i o n s and
e n e r g i e s m a n y r e s e a r c h w o r k e r s wrongly concluded that they had obtained
v e r y s h o r t p u l s e s and v e r y high p o w e r s . It w a s only with t h e d e v e l o p m e n t
of d i r e c t p h o t o e l e c t r i c m e a s u r e m e n t t e c h n i q u e s that t h e s e d i f f i c u l t i e s w e r e
f i n a l l y r e a l i z e d . T h e c o r r e c t i n t e r p r e t a t i o n of t h e m o d e - l o c k i n g p r o c e s s
in l a s e r s with s a t u r a b l e a b s o r b e r s w a s f i r s t put f o r w a r d by Letokhov [46, 47]
who showed t h a t t h e p i c o s e c o n d p u l s e s a r i s e f r o m photon f l u c t u a t i o n s . T h e
3 17
IAEA-SMR-12/31, 32
s a t u r a b l e a b s o r b e r in t h i s p i c t u r e m e r e l y s e l e c t s out t h e m o s t i n t e n s e
f l u c t u a t i o n b u r s t s in a m u l t i m o d e l a s e r r a d i a t i o n f i e l d . When the f l a s h l a m p
i s s w i t c h e d on t h e r e will be no r a d i a t i o n i n s i d e the l a s e r cavity but u n d e r
o p t i c a l p u m p i n g t h e r e will be t h e n o r m a l s p o n t a n e o u s l y e m i t t e d f l u o r e s c e n c e
s p e c t r u m of the a c t i v e m e d i u m . As soon a s t h e r e i s gain in the l a s e r
c a v i t y , a m p l i f i c a t i o n of the " n o i s e r a d i a t i o n " will o c c u r and g r a d u a l l y the
r a d i a t i o n field will b e c o m e p e r i o d i c a l l y c o r r e l a t e d at t i m e s t and t + T ,
w h e r e T i s the double t r a n s i t t i m e . T h i s c o r r e l a t i o n o c c u r s b e c a u s e of
m u l t i p l e r e f l e c t i o n s by the l a s e r m i r r o r s . T h e t o t a l width of the l a s e r
s p e c t r u m w i l l s t i l l be t h a t of t h e l a s e r t r a n s i t i o n band Av{ and the s h a r p e s t
s p i k e s w i l l have a d u r a t i o n At ~1/Ai> f . T h e p r e s e n c e of the p e r i o d i c
c o r r e l a t i o n i s e q u i v a l e n t to having a n u m b e r of d i s c r e t e m o d e s c o n s i s t i n g
of e q u i d i s t a n t g r o u p s of f r e q u e n c i e s given by = I/Q + m / T . Thus we can
c o n n e c t the c o n c e p t s of g r o w t h of p i c o s e c o n d p u l s e s out of photon n o i s e
s t r u c t u r e and the a c t i v e m o d e - l o c k i n g of a l a s e r by the g e n e r a t i o n of
p.m.
FIG. 14. M o d e - l o c k e d n e o d y m i u m : glass l a s e r s y s t e m w i t h s i n g l e p u l s e s e l e c t i o n and a m p l i f i c a t i o n for

m e a s u r e m e n t s of t w o - p h o t o n f l u o r e s c e n c e c r o s s - s e c t i o n s .
F I G . 15. M o d e - l o c k e d p u l s e t r a i n f r o m n e o d y m i u m : glass l a s e r , w i t h s i n g l e u l t r a - s h o r t pulse s w i t c h e d o u t .

3 3 0 BRADLEY
s i d e b a n d s at the i n t e r m o d e s e p a r a t i o n [48]. In g e n e r a l , the f o r m a t i o n of the

q u a s i - p e r i o d i c f l u c t u a t i o n s c a r r i e s on until l a s e r t h r e s h o l d i s r e a c h e d and
t h e i n i t i a l f l u c t u a t i o n s i n f l u e n c e the f o r m of t h e f i n a l t e m p o r a l p a t t e r n of
the r a d i a t i o n . When t h r e s h o l d i s p a s s e d l i n e a r a m p l i f i c a t i o n l e a d s to
f r e q u e n c y n a r r o w i n g , with an i n c r e a s e in the r a n d o m p u l s e d u r a t i o n s . Soon
the s a t u r a b l e a b s o r b e r i s b l e a c h e d and one o r m o r e u l t r a - s h o r t b u r s t s a r e
s e l e c t e d out and a m p l i f i e d to p r o d u c e the m o d e - l o c k e d p u l s e t r a i n , a f t e r
f u r t h e r a m p l i f i c a t i o n in t h e a c t i v e m e d i u m . T h e p r e c i s e d e t a i l s of t h e s e
s e l e c t i o n and a m p l i f i c a t i o n p r o c e s s e s in n e o d y m i u m l a s e r s have been
c a r e f u l l y s t u d i e d both t h e o r e t i c a l l y and e x p e r i m e n t a l l y [49-52] and it i s
s u f f i c i e n t to s t a t e h e r e t h a t the o c c u r r e n c e of a r e g u l a r t r a i n of s i n g l e
u l t r a - s h o r t p u l s e s i s a random, p r o c e s s but that the r e p r o d u c i b i l i t y can
be i m p r o v e d by w o r k i n g c l o s e to t h r e s h o l d , with a low d e n s i t y of the
b l e a c h a b l e dye [ 5 0 ] . C a r e f u l c o n t r o l of the o p e r a t i n g v o l t a g e , the wedging
of all o p t i c a l c o m p o n e n t s in the c a v i t y , the u s e of an o p t i c a l l y c o n t a c t e d
dye c e l l [53] and s e l e c t i o n of p u l s e s f r o m the beginning of the t r a i n [54]
all l e a d to t h e r o u t i n e p r o d u c t i o n of p u l s e s of d u r a t i o n < 1 0 p s .
FIG. 16. T w o - p h o t o n f l u o r e s c e n c e p a t t e r n m e a s u r e m e n t of u l t r a - s h o r t l a s e r p u l s e s .
1. 5. M e a s u r e m e n t of p i c o s e c o n d p u l s e d u r a t i o n s
The widely e m p l o y e d t w o - p h o t o n f l u o r e s c e n c e m e t h o d [55] of u l t r a -

s h o r t p u l s e d u r a t i o n m e a s u r e m e n t u s e s the e x p e r i m e n t a l a r r a n g e m e n t
shown in F i g . 16. E a c h p u l s e of a t r a i n , o r a single s w i t c h e d out p u l s e ,
i s s p l i t into two p u l s e s of e q u a l i n t e n s i t y which, in t h e u s u a l t r i a n g u l a r
a r r a n g e m e n t , o v e r l a p in a c e l l c o n t a i n i n g a dye which can be e x c i t e d to
f l u o r e s c e n c e only by t w o - p h o t o n a b s o r p t i o n at the l a s e r w a v e l e n g t h . The
i n t e n s i t y of t h e f l u o r e s c e n c e s u b s e q u e n t l y e m i t t e d i s t h e n p r o p o r t i o n a l to
the s q u a r e of the i n t e n s i t y of t h e exciting r a d i a t i o n . At the c e n t r e of the
dye c e l l t h e i n t e n s i t i e s of t h e two p u l s e s add to e n h a n c e the f l u o r e s c e n c e .
T h e p h o t o g r a p h e d f l u o r e s c e n c e i n t e n s i t y at a point d i s t a n t Z f r o m t h e m i d -
point of t h e dye c e l l i s given by
IAEA-SMR-12/32, 35 331
1(т) = A J (I(t)} 2 dt + 2 J I(t) I(t + t ) dt (1)

- OO _ CO
w h e r e A i s a c o n s t a n t of p r o p o r t i o n a l i t y and т = 2 Z / C . In d e r i v i n g (1) we
a s s u m e t i m e a v e r a g i n g by t h e p h o t o g r a p h i c p r o c e s s and s p a t i a l a v e r a g i n g
o v e r s e v e r a l o p t i c a l w a v e l e n g t h s , b e c a u s e of t h e l i m i t e d s p a t i a l r e s o l u t i o n
of t h e f i l m . T h e g r e a t a d v a n t a g e of t h i s p u l s e d u r a t i o n m e a s u r e m e n t
t e c h n i q u e i s t h a t t h e s p a t i a l d i s t r i b u t i o n of t h e f l u o r e s c e n c e i s d i r e c t l y
r e l a t e d t o t h e s e c o n d - o r d e r c o r r e l a t i o n f u n c t i o n G 2 (T) s i n c e E q . (1) c a n be
rewritten as
I(T) = A{G 2 (0) + 2G 2 (T)} (2)
with
+ «
G2(T) = J I(t) l(t + T) dt (3)
The complete pulse autocorrelation profile is t h e r e f o r e displayed s i m u l -

t a n e o u s l y a s a f u n c t i o n of d i s t a n c e . S i n c e f a r away f r o m t h e r e g i o n of o v e r l a p
G 2 (T) b e c o m e s z e r o it i s e a s y to s e e t h a t t h e p e a k - t o - b a c k g r o u n d c o n t r a s t
r a t i o , R , of t h e t w o - p h o t o n f l u o r e s c e n c e (TPF) p a t t e r n , w h i c h i s g i v e n by
R ее I(0)/I(°°) (4)
h a s t h e v a l u e 3. W h e n t h e l a s e r r a d i a t i o n i s not a s e r i e s of s i n g l e , i s o l a t e d
p u l s e s but i s s i m p l y a b u r s t of n a r r o w - b a n d r a d i a t i o n n o i s e t h e r e w i l l s t i l l
be a p e a k at т = 0 in t h e T P F p a t t e r n , due t o t h e o v e r l a p of i n d i v i d u a l
FIG. 17. M i c r o d e n s i t o m e t e r t r a c e s of TPF t r a c k s of "noise b u r s t " p u l s e and also a single u l t r a - s h o r t ( ~ 3 ps)

pulse f r o m a m o d e - l o c k e d Nd: glass l a s e r .
332 BRADLEY
FIG.18. S c h e m a t i c d i a g r a m of e x p e r i m e n t a l a r r a n g e m e n t f o r studying a m p l i t u d e f l u c t u a t i o n s of p i c o s e c o n d
pulse t r a i n . In t h e c o n v e n t i o n a l t r i a n g u l a r c o n f i g u r a t i o n on t h e l e f t t h e TPF c e l l is s i t u a t e d a t t h e p o i n t w h e r e
e a c h pulse o v e r l a p s w i t h i t s e l f . In t h e a r r a n g e m e n t on the r i g h t t h e c e l l is s i t u a t e d w h e r e p u l s e s o v e r l a p w i t h
their two nearest neighbours. The distance L equals the laser c a v i t y l e n g t h .
FIG. 19. S i m u l t a n e o u s l y r e c o r d e d TPF p r o f i l e s using t h e a r r a n g e m e n t of F i g u r e 1 8 . T h e p r o f i l e s arise

r e s p e c t i v e l y f r o m t h e o v e r l a p p i n g of e a c h pulse w i t h itself and f r o m t h e o v e r l a p p i n g of e a c h pulse w i t h its
two nearest neighbours. T h e step on t h e r i g h t h a n d side d e f i n e s a c o n t r a s t r a t i o of 2 . 0 .
f l u c t u a t i o n s with t h e m s e l v e s . It h a s been shown [ 56-58] t h a t f o r a long

b u r s t of n o i s e t h e c o n t r a s t r a t i o h a s t h e v a l u e 1.5. F o r a s h o r t b u r s t of n o i s e
(not a s i n g l e t r a n s f o r m l i m i t e d p u l s e ) while the p e a k to b a c k g r o u n d c o n t r a s t
r a t i o i s 3, t h e T P F p a t t e r n h a s a b r o a d b a s e r e p r e s e n t i n g the t o t a l d u r a t i o n
of the b u r s t with a fine " n o i s e s p i k e " s u p e r i m p o s e d . F i g u r e 17 w a s the f i r s t
p h o t o g r a p h [59] of a T P F p r o f i l e showing t h i s f e a t u r e . T h e m e a s u r e d
p e a k : s h o u l d e r : b a s e line r a t i o s w e r e 2 . 6 : 1 . 9 : 1 c o m p a r e d to t h e t h e o r e t i c a l
v a l u e s of 3:2:1 [60] . The width of t h e fine spike v a r i e d f r o m 0.2 p s to 1 p s
I A E A - S M R - 1 2 / 3 2 , 35 3 3 3
but w a s a l w a y s c o r r e l a t e d with t h e s i m u l t a n e o u s l y r e c o r d e d l a s e r s p e c t r a l
w i d t h s of 150A to 30 A. A l s o shown in F i g . 17 i s a s i n g l e p u l s e of d u r a t i o n
3 p s with a l m o s t the t h e o r e t i c a l c o n t r a s t r a t i o . E x p e r i m e n t a l proof that
the s u b p i c o s e c o n d s t r u c t u r e a r o s e f r o m q u a s i - r a n d o m f l u c t u a t i o n s and that
t h e p u l s e s exhibit a p a r t i a l l i n e a r f r e q u e n c y s w e e p w a s obtained with t h e
a r r a n g e m e n t [61] shown in F i g . 18. A f t e r dividing the l a s e r output with a
50% b e a m s p l i t t e r , one b e a m w a s f o c u s s e d into the u s u a l T P F t r i a n g u l a r
s y s t e m while the o t h e r p a s s e d t h r o u g h a s e c o n d T P F dye c e l l and w a s
r e f l e c t e d back on i t s e l f by a 100% m i r r o r p l a c e d at a d i s t a n c e e q u a l to t h e
l a s e r c a v i t y o p t i c a l l e n g t h L . L e n s e s L i and L 2 c o m p e n s a t e d f o r b e a m
d i v e r g e n c e and t o g e t h e r with l e n s L 3 p r e v e n t e d f e e d b a c k into the l a s e r
c a v i t y , which would have p r e v e n t e d good m o d e - l o c k i n g . A 400 ц т p a s s i v e
Q - s w i t c h i n g dye c e l l , in o p t i c a l c o n t a c t with the l a s e r 100% m i r r o r ,
g e n e r a t e d p u l s e s of d u r a t i o n b e t w e e n 10 and 15 p s . F i g u r e 19 shows t h a t
the c e n t r a l f i n e s p i k e ( ~ 0 . 2 ps) i s p r e s e n t only in the p a t t e r n p r o d u c e d in
t h e t r i a n g u l a r a r r a n g e m e n t and t h e c o n t r a s t r a t i o (—2.5) i s a p p r e c i a b l y
g r e a t e r than that of t h e o t h e r p a t t e r n ( ~ 1 , 6 ) . T h e s e s i g n i f i c a n t l y d i f f e r e n t
v a l u e s of the c o n t r a s t r a t i o , and the a b s e n c e of t h e fine s p i k e in the s e c o n d
p a t t e r n , i n d i c a t e d t h a t the p u l s e s contained r a n d o m n o i s e fluctuations; on a
picosecond time scale.
E a r l y r e p o r t s of s u b p i c o s e c o n d p u l s e s f r o m n e o d y m i u m : g l a s s l a s e r s
and of ~ 5 p i c o s e c o n d p u l s e s f r o m r u b y l a s e r s w e r e b a s e d upon T P F p a t t e r n s
in which only the n o i s e s p i k e w a s m e a s u r e d . U n f o r t u n a t e l y , t h i s h a s led
to o v e r o p t i m i s t i c e x p e c t a t i o n s f o r the u s e of t h e s e l a s e r s in e x p e r i m e n t s
involving the m e a s u r e m e n t of p i c o s e c o n d p h e n o m e n a . The s i t u a t i o n i s
f u r t h e r c o m p l i c a t e d by the e f f e c t of f l u o r e s c e n c e quenching u n d e r
e x c i t a t i o n of i n t e n s e l a s e r r a d i a t i o n [44, 62] which l e a d s to a r e v e r s a l of
the T P F " n o i s e s p i k e " as s e e n in F i g . 20. In s u m m a r y , t h e T P F d i s p l a y
FIG. 20. M i c r o d e n s i t o m e t e r t r a c e showing r e v e r s a l of TPF " n o i s e s p i k e " of a ruby l a s e r pulse t r a i n a t h i g h

laser powers. N o r m a l TPF p a t t e r n is o n r i g h t .
3 3 4 BRADLEY
t e c h n i q u e d o e s not uniquely d e f i n e the s h a p e of t h e l a s e r p u l s e . M o r e o v e r

it i s not p o s s i b l e to m e a s u r e low i n t e n s i t y p u l s e s , and the p r e s e n c e of a
s u b s t a n t i a l p r o p o r t i o n of the l a s e r e n e r g y o u t s i d e the u l t r a - s h o r t p u l s e s
t h e m s e l v e s i s not r e c o r d e d . T h e s e d e f e c t s have been o v e r c o m e by the
d e v e l o p m e n t of d i r e c t p h o t o e l e c t r i c m e a s u r e m e n t e m p l o y i n g e l e c t r o - o p t i c a l
streak c a m e r a s . Before discussing these latest developments frequency
t u n a b l e m o d e - l o c k e d dye l a s e r s will be d e s c r i b e d s i n c e it w a s the a v a i l a b i l i t y
of p u l s e s of ~2 ps d u r a t i o n f r o m t h e s e l a s e r s t h a t m a d e p o s s i b l e the t e s t i n g
and e v a l u a t i o n of the p i c o s e c o n d s t r e a k c a m e r a s .
1.6. F r e q u e n c y - t u n a b l e m o d e - l o c k e d dye l a s e r s
While the f i r s t f l a s h l a m p - p u m p e d R h o d a m i n e dye l a s e r s to be p a s s i v e l y

m o d e - l o c k e d [41, 42] p r o d u c e d p u l s e s of d u r a t i o n s < 5 p s , the l a s e r s p e c t r a l
b a n d w i d t h s of 3 - 1 0 nm w e r e up to 100 t i m e s g r e a t e r than t h e F o u r i e r l i m i t
s e t by the p u l s e d u r a t i o n s . T h i s d i s c r e p a n c y had a l r e a d y been m e t with in
n e o d y m i u m : g l a s s l a s e r s but, unlike N d : g l a s s , o r g a n i c dye s o l u t i o n s a r e
h o m o g e n e o u s l y b r o a d e n e d and the n o r m a l b r o a d b a n d s p e c t r a l output can
MODE - LOCKING
MIRROR
FIG.21. Mode-locked, flashlamp-pumped, frequency-tunable dye laser.
0 SEALS
i
• S E C U R IN G
+ VE HT г -
F = 3
.SCREWS
TRIGGER
m
PIN'
TRIGGER
\TOLTAGE
3 QUARTZ FLASHLAMP SPARK PLUG
UMWf*l—-J— ^STAINLESS
BLOCK
NYLON ' WALLS OF ELLIPTICAL-
REFLECTOR -VE HT
TO V A C U U M PUMP
FIG.22. Gigawatt ablative flashlamp.

I A E A - S M R - 1 2 / 3 2 , 35 335
Rhod a m i n e 6G
-i Ф
О- и
•г г»
ОО j.
ЗШГ 50ТГ
W a v e l e n g t h (nm)
FIG. 23. A b s o r p t i o n and f l u o r e s c e n c e of R h o d a m i n e 6 G .
be n a r r o w e d , a s we have s e e n , with l i t t l e e n e r g y l o s s , by the i n s e r t i o n of

d i s p e r s i v e e l e m e n t s i n s i d e the l a s e r c a v i t y . T h e p u l s e b a n d w i d t h - d u r a t i o n
d i s c r e p a n c y of p i c o s e c o n d p u l s e s w a s r e m o v e d by f r e q u e n c y n a r r o w i n g a
m o d e - l o c k e d R h o d a m i n e 6G dye l a s e r with a s i n g l e F a b r y - P e r o t i n t e r -
f e r o m e t e r f i l t e r which a l s o p e r m i t t e d f r e q u e n c y - t u n i n g of the p i c o s e c o n d
p u l s e s o v e r a r a n g e of 2 3 n m , w i t h o u t any a p p r e c i a b l e c h a n g e s in the p u l s e
d u r a t i o n s o r l i n e w i d t h s . The m o d e - l o c k e d dye l a s e r a r r a n g e m e n t i s shown
in F i g . 21 and d e t a i l s of the l a s e r head and f l a s h t u b e can be s e e n in F i g . 22.
A 1.5 xlO" 4 M. solution of R h o d a m i n e 6G, w h o s e a b s o r p t i o n bands m a t c h t h e
f l a s h l a m p output s p e c t r u m ( F i g . 23), c i r c u l a t i n g in a 6 m m d i a m e t e r 21 c m
long q u a r t z c e l l , w a s p u m p e d by à l i n e a r a b l a t i v e a i r f l a s h l a m p in an
e l l i p t i c a l p u m p i n g r e f l e c t o r . Highly r e p r o d u c i b l e m o d e - l o c k i n g w a s a c h i e v e d
in a 50 c m l a s e r c a v i t y , with 100% and 65% r e f l e c t i v i t y , wedged, d i e l e c t r i c
m i r r o r s , by a 10" 4 M. s o l u t i o n of 3,3' d i e t h y l o x a d i c a r b o - c y a n i n e iodide
(DODCI) ( F i g . 24) in e t h a n o l in a 2 m m path l e n g t h c e l l in o p t i c a l c o n t a c t
with the 100% m i r r o r . F r e q u e n c y n a r r o w i n g and tuning w a s obtained with
a 8 ix m gap wedged F a b r y - P e r o t e t a l o n . Without the e t a l o n t h e m o d e - l o c k e d
l a s e r s p e c t r u m s h i f t e d to the r e d but by a d j u s t i n g the p u m p i n g e n e r g y to
k e e p o p e r a t i n g j u s t above t h r e s h o l d tuning with the i n t e r f e r o m e t e r f r o m
602 to 62 5 nm w a s a c h i e v e d with a c o n s t a n t bandwidth of ~ 0 . 2 nm ( F i g . 2 5).
The untuned m o d e - l o c k e d l a s e r e m i t t e d a 600 n s p u l s e t r a i n with a t o t a l
e n e r g y of 50 m j ( F i g . 26). When f r e q u e n c y n a r r o w e d and tuned t h e p u l s e
t r a i n s s h o r t e n e d to 200 n s (55 p u l s e s ) and the e n e r g y p e r p u l s e w a s r e d u c e d
to 2 x 10" 3 m j at 62 5 n m and to 5 x 10~3 m j at 605 n m . P u l s e d u r a t i o n s w e r e
obtained by the t w o - p h o t o n f l u o r e s c e n c e t e c h n i q u e ( F i g . 2 7) u s i n g a s a t u r a t e d
3 3 6 BRADLEY
I С -ICH = CH)n - CH = С N I
N+ ' N
I I
L R R
GENERAL FORMULA FOR POLYMET H I N E S
n - integer 2 — various structures
R — alkyl radical
О
0 Q H C H = CH,2-CH=<°}Q OOOC I
CjHs c'2Hs
Q ( ° y . C H = C H , 3 - C H = ( ° ) Q DOTC I
CjHs CjHs
O C NI V , c H = c H > r C H = IC ^ O DTDC I
C2H5 CjHs
DDCI
O C ^ < C H = CH)j - C H с, H5
O O
-ICH-CH) -CH
N
I
X> I DOTCI
C2H5
с, H.
FIG.24. Polymethine dyes.
solution of d i m e t h y l P O P O P in benzene and an i m a g e i n t e n s i f i e r f o r photo-

graphy of the t r a c k s . M i c r o d e n s i t o m e t e r t r a c e s of T P F p r o f i l e s and l a s e r
s p e c t r a ( s i m u l t a n e o u s l y r e c o r d e d ) n e a r the ends of the tuning r a n g e a r e shown
in F i g . 28. The l a s e r p u l s e duration — s p e c t r a l bandwidth product Ai/At = 0.5
and the p u l s e s a r e of t r a n s f o r m limited d u r a t i o n s . T P F m e a s u r e m e n t s made
throughout the tuning r a n g e c o n f i r m e d that the pulse d u r a t i o n s w e r e between
2 and 4 p s . F i g u r e 27 a l s o shows that the s p e c t r a l band widths a r e a l s o l a r g e l y
independent of l a s i n g w a v e l e n g t h s .
When the l a s e r was pumped above t h r e s h o l d s p e c t r a l broadening
o c c u r r e d . The l a s e r band width broadened with i n c r e a s i n g pump power to
a width of 1.2 nm which i s ~75% of the h a l f - w i d t h of the e t a l o n f i l t e r .
Build-up of f r e q u e n c y broadening was a l s o s e e n by examining the t i m e
d e v e l o p m e n t of the l a s e r s p e c t r a l output with a s t r e a k c a m e r a (Fig. 29).
S p e c t r a of p u l s e s switched out f r o m d i f f e r e n t p a r t s of the m o d e - l o c k e d t r a i n
a l s o showed that the s p e c t r a l broadening i n c r e a s e d monotonically along the
t r a i n with i n c r e a s i n g p u l s e intensity. The two s p e c t r a shown in F i g . 30
w e r e obtained f r o m p u l s e s switched out 30 ns and 120 n s , r e s p e c t i v e l y .
I A E A - S M R - 1 2 / 3 2 , 35 3 3 7
FIG. 25. S p e c t r a showing t u n i n g of t r a n s f o r m l i m i t e d p i c o s e c o n d p u l s e s . M e r c u r y c a l i b r a t i o n s p e c t r u m is

at t o p . P l a t e of 1 m e t r e s p e c t r o g r a p h w a s m o v e d v e r t i c a l l y as l a s e r w a s tuned f r o m 6 0 3 to 625 n m .
FIG.26. O s c i l l o g r a m s of m o d e - l o c k e d d y e l a s e r .
3 3 8 BRADLEY
FIG.21. T w o - p h o t o n f l u o r e s c e n c e m i c r o d e n s i t o m e t e r t r a c e of d y e l a s e r p u l s e s .
FIG. 2 8 . M i c r o d e n s i t o m e t e r t r a c e s of t w o p a i r s of s i m u l t a n e o u s l y r e c o r d e d TPF t r a c k s a n d s p e c t r a of t r a n s f o r m
l i m i t e d R h o d a m i n e 6G p i c o s e c o n d p u l s e s . TOP Spectral width 0 . 2 4 n m at 605 n m . Pulse d u r a t i o n 3 p s .
BOTTOM Spectral width 0 . 1 8 nm at 6 2 4 . 6 n m . Pulse d u r a t i o n 4 ps. All ordinates are l i n e a r density scales.
IAEA-SMR-12/31, 32 3 3 9
Time
X 1 nm
FIG.29. S t r e a k p h o t o g r a p h of the s p e c t r a l o u t p u t of R h o d a m i n e 6G d y e l a s e r m o d e - l o c k e d a t 607 n m showing

the i n i t i a l s t a g e s of m o d e - l o c k i n g .
WAVELENGTH
4 h-
0-2 nm
FIG. 30. M i c r o d e n s i t o m e t e r t r a c e s of s p e c t r a of s w i t c h e d o u t p i c o s e c o n d p u l s e s : (a) a p p r o x i m a t e l y 50 pulses

f r o m s t a r t of t r a i n ; (b) a t b e g i n n i n g of pulse t r a i n .
3 4 0 BRADLEY
f r o m t h e s t a r t of t h e p u l s e t r a i n with the l a s e r o p e r a t i n g at 607 n m . This

frequency broadening a r i s e s f r o m self-phase-modulation arising f r o m
n o n - l i n e a r r e f r a c t i v e index c h a n g e s in the ethanol s o l v e n t . F r o m t h e
r e l a t i o n s h i p s [43]
ón = n 2 E 2 (5)
and
6v = 2 i ó n / A A t (6)
f o r t h e f r e q u e n c y b r o a d e n i n g bv, a r i s i n g f r o m the l a s e r i n t e n s i t y E 2 ,
(n 2 i s the n o n - l i n e a r index of r e f r a c t i o n , X i s the l a s e r w a v e l e n g t h and At
i s the p u l s e d u r a t i o n ) and the s p e c t r a shown in F i g s 29 and 30 it w a s p o s s i b l e
to c a l c u l a t e [43] the value n 2 = 10" 18 cm 2 • V" 2 f o r e t h a n o l . T h e s e r e s u l t s
showed that in the m o d e - l o c k e d dye l a s e r the p u l s e b a n d w i d t h - d u r a t i o n
d i s c r e p a n c y a r o s e f r o m s e l f - p h a s e m o d u l a t i o n and t h a t t h i s can be avoided
by f r e q u e n c y n a r r o w i n g with an etalon f i l t e r and o p e r a t i n g at t h r e s h o l d .
С ^
V's\ V A
I \ Ч
' Í ' \
r /
/
\ /
>v
/
500 520 540 600 620 640
Wavelength (nm)
FIG. 31. N o r m a l i z e d f l u o r e s c e n c e s p e c t r a of l a s e r dye s o l u t i o n s , (a) R h o d a m i n e 6G; (b) R h o d a m i n e В;

(с) C r e s y l V i o l e t . S h o w n d o t t e d are t h e n o r m a l a b s o r p t i o n s p e c t r a of t h e m o d e - l o c k i n g p o l y m e t h i n e d y e s .
(1) D O D C I ; (2) D Q T C I ; (3) D T D C I ; (4) D D C I .
T A B L E I, LASER TUNING RANGES
Laser d y e S a t u r a b l e absorber Mode-locked tuning range (nm)
R h o d a m i n e 6G DODCI 584 - 625
Rhodamine В DQTCI 6 0 5 - 639

DODCI 615 - 645
Cresyl-violet DTDCI 652 - 704

+ R h o d a m i n e 6G DDCI 6 4 4 - 680
DOTCI 644 - 680
I A E A - S M R - 1 2 / 3 2 , 35 341
A l t e r n a t i v e l y t r a n s f o r m - l i m i t e d p u l s e s can be s w i t c h e d out f r o m the beginning

of a t r a i n b e f o r e f r e q u e n c y b r o a d e n i n g builds up.
By e m p l o y i n g o t h e r p o l y m e t h i n e d y e s a s s a t u r a b l e a b s o r b e r s f o r
R h o d a m i n e В, R h o d a m i n e 6G and c r e s y l - v i o l e t d y e s , p i c o s e c o n d p u l s e s of
d u r a t i o n s 3 - 5 ps have been g e n e r a t e d [63] c o v e r i n g the s p e c t r a l r e g i o n
590 n m to 704 n m . F i g u r e 31 s h o w s the n o r m a l i z e d f l u o r e s c e n c e s p e c t r a
of the l a s e r d y e s and the a b s o r p t i o n s p e c t r a of t h e p o l y m e t h i n e d y e s e m p l o y e d
a s m o d e - l o c k e r s . The s p e c t r a l r a n g e s c o v e r e d by v a r i o u s c o m b i n a t i o n s
of l a s i n g d y e s and s a t u r a b l e a b s o r b e r s a r e shown in T a b l e I.
These tunable frequency picosecond pulses f r o m flashlamp pumped
dye l a s e r s can a l s o be a m p l i f i e d by s e l e c t i n g out a s i n g l e - p u l s e f r o m t h e
beginning of a t r a i n as shown in F i g . 32 and t h r o u g h a dye a m p l i f i e r [91] .
H o w e v e r , b e c a u s e of the s h o r t s t o r a g e t i m e s of the dye m o l e c u l e s (typically
< 5 ns) s a t u r a t i o n of the a m p l i f i e r quickly o c c u r s (Fig. 33). N e v e r t h e l e s s ,
it i s p o s s i b l e to obtain > 1 GW p e a k p o w e r p u l s e s in t h i s m a n n e r .
CW dye l a s e r s have a l s o b e e n m o d e - l o c k e d by e m p l o y i n g i n t r a c a v i t y
m o d u l a t o r s [64, 65] to p r o d u c e p u l s e s of d u r a t i o n s ~ 5 5 p i c o s e c o n d s [64] .
P a s s i v e m o d e - l o c k i n g of R h o d a m i n e 6G CW l a s e r s h a s a l s o been o b t a i n e d
with the s a m e m o d e - l o c k i n g dye (DODCI) e m p l o y e d with p u l s e d l a s e r s .
TO PD2
HA L F - W /
PLATE
INPUT PULSE
TO
PD I
AMPLIFYING DYE
CELL
СA LIBRATED
FILTERS
FIG.32. M e t h o d of s w i t c h i n g o u t and a m p l i f y i n g t u n a b l e f r e q u e n c y d y e l a s e r p i c o s e c o n d p u l s e .
BRADLEY
SMALL SIGNAL AMPLIFICATION
TIME (/usee) —
FIG.33. Saturation of a m p l i f i c a t i o n of a single picosecond pulse f r o m a m o d e - l o c k e d d y e l a s e r .
FIG.34. M o d e - l o c k e d CW dye l a s e r showing m o n i t o r i n g a r r a n g e m e n t s .

I A E A - S M R - 1 2 / 3 2 , 35 343
FIG. 35. C W m o d e - l o c k e d d y e l a s e r pulse t r a i n . Each m a j o r division represents 4 ns. (Sub-pulses are due
to e l e c t r i c a l r i n g i n g in t h e p h o t o - d e t e c t o r c i r c u i t . )
With a dye l a s e r pumped by a CW a r g o n l a s e r and e m p l o y i n g a folded

o p t i c a l cavity with two b e a m w a i s t s , one in t h e R h o d a m i n e 6G c e l l and a
s e c o n d in t h e s a t u r a b l e a b s o r b e r c e l l , p u l s e d u r a t i o n s of ~ 2 p s have been
m e a s u r e d with c o r r e l a t i o n t e c h n i q u e s b a s e d upon s e c o n d - h a r m o n i c
g e n e r a t i o n [ 6 6 ] . With the a r r a n g e m e n t shown in F i g . 34 p a s s i v e m o d e - l o c k i n g
of a CW T h o d a m i n e l a s e r h a s a l s o been a c h i e v e d [33, 6 7 ] . The DODCI
s a t u r a b l e a b s o r b e r i s in c o n t a c t with the 100% r e f l e c t i v i t y m i r r o r . The
r e s u l t i n g p u l s e t r a i n ( F i g . 35) i s d e t e c t e d with a f a s t photodiode. The
o s c i l l o g r a m p u l s e r i s e - t i m e s a r e d e t e c t o r l i m i t e d and when m e a s u r e d with
a s t r e a k c a m e r a ( s e e next s e c t i o n ) p u l s e d u r a t i o n s of < 5 p i c o s e c o n d s w e r e
o b t a i n e d . P e a k p o w e r s of ~ 1 0 0 w a t t s a r e o b t a i n a b l e f r o m t h e s e CW
t r a i n s of tunable f r e q u e n c y p u l s e s .
1. 7. D i r e c t p h o t o e l e c t r i c m e a s u r e m e n t s of p i c o s e c o n d p u l s e s
The s i m p l e s t and m o s t d i r e c t m e t h o d of r e c o r d i n g the i n t e n s i t y p r o f i l e

of a light p u l s e i s p r o v i d e d by the p h o t o d i o d e - o s c i l l o s c o p e c o m b i n a t i o n .
While the r e s p o n s e t i m e of the p h o t o e l e c t r i c e f f e c t i s < 10" 14 s [68] t h e
f a s t e s t r e a l - t i m e o s c i l l o s c o p e s have band widths of 5 GHz, (for a s e n s i t i v i t y
of 35 V- cm" 1 ), c o r r e s p o n d i n g to a r i s e t i m e of ~ 7 0 p s . Photodiodes with
r i s e t i m e s —100 ps and with c u r r e n t c h a r a c t e r i s t i c s c a p a b l e of d r i v i n g s u c h
an o s c i l l o s c o p e a r e c o m m e r c i a l l y a v a i l a b l e . R e c e n t l y a 10 GHz I M P A T T
s i l i c o n photodiode m o u n t e d in a c o - a x i a l c a b l e h a s been e m p l o y e d to d r i v e
a 5-GHz o s c i l l o s c o p e with a s e n s i t i v i t y of 3 V- cm" 1 [ 6 9 ] . When r e a l - t i m e
m e a s u r e m e n t i s not r e q u i r e d the u s e of p u l s e - s a m p l i n g t e c h n i q u e s can be
applied to m e a s u r e m e n t s of the d u r a t i o n s of r e p e t i t i v e p u l s e s s u c h a s
p r o d u c e d by CW m o d e - l o c k e d l a s e r s . The photodiode r i s e t i m e then l i m i t s
the t i m e - r e s o l u t i o n a c h i e v e d [ 33, 64] to ~ 1 0 0 ps s i n c e the o s c i l l o s c o p e
s a m p l i n g unit can have a r i s e t i m e a s s h o r t a s 25 p s . T h u s f o r the h i g h -
p o w e r light p u l s e s p r o d u c e d by m o d e - l o c k e d l a s e r s d i r e c t m e a s u r e m e n t
344 BRADLEY
of p u l s e d u r a t i o n s to a t i m e - r e s o l u t i o n l i m i t of ~ 1 0 0 ps can be r e a d i l y
a c h i e v e d . H o w e v e r , a t i m e - r e s o l u t i o n of ~ 1 ps i s r e q u i r e d f o r l a s e r p u l s e
d i a g n o s i s and t h i s c a n only be a c h i e v e d with e l e c t r o n - o p t i c a l c h r o n o g r a p h y [70].
1.8. Electron-optical chronography
The m e t h o d of s t u d y i n g r a p i d l y changing l u m i n o u s p h e n o m e n a by
e l e c t r o n - o p t i c a l c h r o n o g r a p h y was f i r s t p r o p o s e d in 1956 [71] by Z a v o i s k i i
and F a n c h e n k o who pointed out that the t i m e - r e s o l u t i o n of an i m a g e - t u b e
s t r e a k c a m e r a i s u l t i m a t e l y l i m i t e d by p h o t o - e l e c t r o n t r a n s i t t i m e s p r e a d
in t h e f i r s t i m a g e - t u b e . This s p r e a d , which a r i s e s f r o m v a r i a t i o n s in
m a g n i t u d e of the i n i t i a l p h o t o - e l e c t r o n v e l o c i t i e s [ 7 2 ] , i s m a i n l y d e v e l o p e d
while the p h o t o - e l e c t r o n s a r e c l o s e to the photocathode w h e r e they a r e
m o v i n g s l o w l y . It can be e a s i l y shown [67, 73, 74] t h a t f o r any e l e c t r o n -
o p t i c a l a r r a n g e m e n t the d i s t r i b u t i o n of p h o t o - e l e c t r o n t r a n s i t t i m e s t h r o u g h
t h e i m a g e tube h a s a h a l f - w i d t h
Atd = mAU/eE (7)
w h e r e AU i s the h a l f - w i d t h of t h e i n i t i a l e l e c t r o n velocity d i s t r i b u t i o n and

E i s the e l e c t r i c field s t r e n g t h n e a r t h e p h o t o c a t h o d e ; e and m a r e the
e l e c t r o n i c c h a r g e and m a s s , r e s p e c t i v e l y . The v a l u e of AU f o r a p a r t i c u l a r
p h o t o c a t h o d e d e p e n d s upon the w a v e l e n g t h of the i l l u m i n a t i n g light. T h u s
f o r a Cs 3 Sb photocathode and light of w a v e l e n g t h 0.53 ßra ( s e c o n d h a r m o n i c
of Nd l a s e r wavelength) the s p r e a d in p h o t o e l e c t r o n e n e r g y h a s a h a l f - w i d t h
of ~ 0 . 3 eV l e a d i n g to a v a l u e 2.3 x 10 7 c m - s" 1 f o r AU. To obtain a t i m e
r e s o l u t i o n of 1 p s then r e q u i r e s a v a l u e E = 13 ООО V- cm" 1 f o r the
p h o t o c a t h o d e e l e c t r i c f i e l d . F o r light p u l s e s of photon e n e r g y 2.0 eV
(X 615 nm) the p h o t o e l e c t r o n e n e r g y s p r e a d i s ~ 0 . 1 eV s o t h a t a photocathode
e l e c t r i c field s t r e n g t h of E = 7500 V- cm" 1 i s s u f f i c i e n t to a c h i e v e t h e s a m e
t i m e r e s o l u t i o n . F r o m t h i s it follows that if a t i m e r e s o l u t i o n l i m i t of
< 1 ps i s to be a c h i e v e d with an e l e c t r o n - o p t i c a l s t r e a k c a m e r a a p h o t o -
c a t h o d e e x t r a c t i o n field of between 8000 V. c m " 1 and 15 000 V- cm" 1 i s
n e e d e d and t h a t the s p e c t r a l r e s p o n s e of t h e photocathode should be m a t c h e d
to t h e w a v e l e n g t h of the light p u l s e s so that t h e p h o t o c a t h o d e i s o p e r a t i n g
a s c l o s e a s p o s s i b l e to i t s long w a v e l e n g t h c u t - o f f . T h u s t h e u l t i m a t e
t i m e - r e s o l u t i o n of the s t r e a k i m a g e - t u b e d e p e n d s upon both t h e type of
p h o t o c a t h o d e and t h e light w a v e l e n g t h a s w e l l as the e x t r a c t i o n e l e c t r i c field
s t r e n g t h . The d e s i g n s of t h e e l e c t r o n - o p t i c s of t h e i m a g e - t u b e s a v a i l a b l e
f o r u s e in h i g h - s p e e d s t r e a k c a m e r a s up to 1970 w e r e s u c h t h a t t h e c a m e r a
i n s t r u m e n t a l f u n c t i o n s had h a l f - w i d t h s in t h e r a n g e 20 p s [75, 76] to 60 p s
[ 7 7 ] . The u s e of a p l a n a r fine m e s h , h i g h - p o t e n t i a l e x t r a c t i o n e l e c t r o d e
p l a c e d c l o s e to t h e photocathode of a s t r e a k i m a g e tube [78] f i r s t p e r m i t t e d
t h e r e d u c t i o n of the t i m e - d i s p e r s i o n r e s o l u t i o n l i m i t to ~ 5 ps [ 7 9 ] . The
e s s e n t i a l c o m p o n e n t s of t h i s s t r e a k c a m e r a s y s t e m and t h e e x p e r i m e n t a l
a r r a n g e m e n t f o r t e s t i n g p e r f o r m a n c e a r e shown in F i g . 36.
S e c o n d - h a r m o n i c p u l s e s g e n e r a t e d f r o m a m o d e - l o c k e d Nd : g l a s s l a s e r
w e r e f i r s t i n j e c t e d into an o p t i c a l delay line c o n s i s t i n g of an a r r a y of
b e a m - s p l i t t e r s , to p r o d u c e f r o m e a c h p u l s e of the t r a i n a s e r i e s of
s u b p u l s e s , with known d e l a y s between t h e m . T h e s e a c c u r a t e l y known d e l a y s
p e r m i t t e d a u t o m a t i c c a l i b r a t i o n and c h e c k i n g of t h e l i n e a r i t y of the c a m e r a
s t r e a k . The s e c o n d - h a r m o n i c b e a m i l l u m i n a t e d a d i f f u s i n g s c r e e n in f r o n t
I A E A - S M R - 1 2 / 3 2 , 35 345
Modified P 856
shutter tube
FIG.36. Experimental a r r a n g e m e n t for testing picosecond streak c a m e r a p e r f o r m a n c e .
of the 5 0 - д т s l i t of the s t r e a k c a m e r a . P a r t of t h e f u n d a m e n t a l l a s e r b e a m
t r i g g e r e d , via a b e a m s p l i t t e r , an i n s u l a t e d s p a r k gap [80] to g e n e r a t e t h e
s t r e a k d e f l e c t i o n voltage r a m p [81] . To avoid i m a g e d i s t o r t i o n and l o s s of
s p a t i a l and t e m p o r a l r e s o l u t i o n a r i s i n g f r o m high p h o t o c u r r e n t d e n s i t i e s
[82] an i m a g e i n t e n s i f i e r t u b e , of f a c t o r - 1 0 6 light gain, w a s o p t i c a l l y coupled
to t h e output p h o s p h o r of the s t r e a k i m a g e t u b e , w h e r e a s t r e a k w r i t i n g
s p e e d of 3.5 x 10 9 c m - s " 1 with a d y n a m i c a l s p a t i a l r e s o l u t i o n of 5 p / m m
w a s o b t a i n e d . The 30 u s d e c a y t i m e of the P l l p h o s p h o r of the s t r e a k tube
r e s u l t s in the r e d u c t i o n by a f a c t o r of 107 of the peak c u r r e n t in the f i r s t
s t a g e of t h e i n t e n s i f i e r . The u s e of t h i s high gain i m a g e i n t e n s i f i e r a l s o
p e r m i t s the r e c o r d i n g of e a c h i n i t i a l p h o t o e l e c t r o n so t h a t weak light p u l s e s
c a n be r e c o r d e d (see below). The s t r e a k p h o t o g r a p h of F i g . 37 and the
c o r r e s p o n d i n g m i c r o d e n s i t o m e t e r t r a c e showed that t h e r e w e r e no s a t e l l i t e
p u l s e s [83, 51] in t h e t r a i n as e x p e c t e d f r o m a l a s e r m o d e - l o c k e d with an
o p t i c a l l y c o n t a c t e d dye c e l l [53] . To a good a p p r o x i m a t i o n the r e c o r d e d
p u l s e h a l f - w i d t h Д т а can be w r i t t e n [84]
(Дт к ) 2 = ( Д т / + ( A t d ) 2 + ( А т / (8)
w h e r e ATS i s the t i m e r e s o l u t i o n l i m i t a r i s i n g f r o m t h e f i n i t e s p a t i a l
r e s o l u t i o n of the i m a g e tube c a m e r a , at a p a r t i c u l a r s t r e a k w r i t i n g r a t e .
AT r a r i s e s f r o m p h o t o e l e c t r o n t r a n s i t t i m e s p r e a d and Д т р i s the l a s e r
p u l s e width. (The s l i t width i s s e t to m a k e n e g l i g i b l e the r e s o l u t i o n l i m i t
f r o m t h i s . ) Using Eq. (7), w r i t i n g Д т 0 = k / E w h e r e к = т Д и / е , and
s u b s t i t u t i n g in (8) gives
(AT r ) 2 = ( Д т / + ( Д т р ) 2 + k 2 / E 2 (9)
By v a r y i n g t h e e x t r a c t i o n m e s h v o l t a g e and h e n c e t h e v a l u e of E an
e x p e r i m e n t a l plot of (AT r )2 a s a f u n c t i o n of E~2 w a s obtained giving a s t r a i g h t
l i n e . The value of (Дт,.) 2 + (Дт Р ) 2 obtained f r o m the i n t e r c e p t on t h e (Дт R ) -
a x i s could then be s u b s t i t u t e d into E q . (8) to give the v a l u e s of Д т 0 c o r r e -
s p o n d i n g to t h e d i f f e r e n t v a l u e s of E e m p l o y e d . The plot of Д т п v e r s u s E" 1
( F i g . 38) w a s a s t r a i g h t line t h r o u g h t h e o r i g i n a s e x p e c t e d f r o m Eq. (7).
3 4 6 BRADLEY
FIG.37. TOP S t r e a k of s u c c e s s i v e slit i m a g e s , f r o m t h e b e a m s p l i t t e r a r r a y , of second h a r m o n i c of a

s i n g l e u l t r a - s h o r t N d : glass l a s e r p u l s e s . S e p a r a t i o n s b e t w e e n s t r e a k e d i m a g e s a r e 150 ps a n d 350 ps,
respectively.
BOTTOM M i c r o d e n s i t o m e t e r t r a c e of s t r e a k p h o t o g r a p h ( o r d i n a t e a r b i t r a r y l i n e a r d e n s i t y s c a l e ) .
T h i s g r a p h p e r m i t t e d the d i r e c t c o m p a r i s o n of the e x p e r i m e n t a l and

p r e d i c t e d v a l u e s of Д т 0 . Substituting into (7) the above value f o r AU g a v e 1
A t d = 4 ps f o r E = 3333 V- cm" 1 in good a g r e e m e n t with the e x p e r i m e n t a l
v a l u e of 5.6 p s .
T h e s e f i r s t r e s u l t s i n d i c a t e d the need f o r h i g h e r m e s h p o t e n t i a l s . New
i m a g e t u b e s d e s i g n e d to o p e r a t e with p h o t o c a t h o d e e x t r a c t i o n f i e l d s of up
1
T h e c a l c u l a t e d v a l u e for Д т ^ i n R e f . [ 8 4 ] w a s t o o l a r g e by x / 2 .
I A E A - S M R - 1 2 / 3 2 , 35 3 4 7
Аг 0
FIG.38. (a) E x p e r i m e n t a l p l o t of (Дтpj 2 as a f u n c t i o n of F''. (b) P l o t of p h o t o e l e c t r o n t r a n s i t t i m e d i s p e r s i o n
A Tp a s a f u n c t i o n of E " 1 .
to 10 ООО V - cm" 1 and with i n c r e a s e d d e f l e c t i o n s e n s i t i v i t y , p e r m i t t e d t h e

c l e a r r e s o l u t i o n of p u l s e s t r u c t u r e s e p a r a t e d by 2.5 ps [32] . To a c h i e v e
t h i s , t h e l a s e r - t r i g g e r e d s p a r k gap w a s r e p l a c e d by an a v a l a n c h e t r a n s i s t o r -
K r y t r o n c i r c u i t ( r e q u i r i n g a t r i g g e r p u l s e of 10 V), to give an i n c r e a s e d
s t r e a k s p e e d > 10 10 c m . s" 1 without l o s s of d y n a m i c s p a t i a l r e s o l u t i o n , and
with a t r i g g e r i n g j i t t e r of ~ 2 0 0 p s . The a v a i l a b i l i t y of f r e q u e n c y t u n a b l e
m o d e - l o c k e d dye l a s e r s [43, 63] c a p a b l e of r e l i a b l y p r o d u c i n g p u l s e s of
3 4 8 BRADLEY
Output Input : Train of Pulses
from Laser
FIG. 39. D i r e c t m e a s u r e m e n t of s t r e a k c a m e r a i n s t r u m e n t a l f u n c t i o n e m p l o y i n g m o d e - l o c k e d d y e l a s e r .
d u r a t i o n 2 ± 1 ps p e r m i t t e d the d i r e c t m e a s u r e m e n t of a s y s t e m t i m e
r e s o l u t i o n l i m i t of ~ 1 ps with t h e a r r a n g e m e n t shown in F i g . 39. Since
the dye l a s e r w a v e l e n g t h ( ~ 6 1 5 nm) w a s c l o s e r to the c u t - o f f w a v e l e n g t h
of t h e CSgSb p h o t o c a t h o d e ( s p r e a d in p h o t o e l e c t r o n e n e r g i e s Д е = 0.1 eV)
a t i m e - d i s p e r s i o n l i m i t of < 1 p s should be obtained with the e x t r a c t i o n field
of 8000 V- cm" 1 . The o p t i c a l delay l i n e w a s a r r a n g e d to p r o d u c e , f r o m a
s i n g l e l a s e r p u l s e , p a i r s of s u b - p u l s e s s e p a r a t e d by 6.6 ps with o t h e r
s u b - p u l s e s s p a c e d 60 p s b e f o r e and a f t e r the c l o s e p a i r . T h e c e n t r a l p a i r ,
shown in F i g . 4 0 , w a s c l e a r l y r e s o l v e d and f r o m the m i c r o d e n s i t o m e t e r t r a c e
t h e r e c o r d e d p u l s e width w a s m e a s u r e d to be 2.5 p s . C l o s e r e x a m i n a t i o n
of the r e c o r d h o w e v e r showed t h a t e a c h a p p a r e n t l y s i n g l e s u b - p u l s e , and
h e n c e t h e o r i g i n a l l a s e r p u l s e f r o m which the s u b - p u l s e s w e r e d e r i v e d ,
w a s i t s e l f a double p u l s e s e p a r a t e d by 2.5 p s . C l e a r r e s o l u t i o n of t h i s
s t r u c t u r e can a l s o be s e e n in F i g . 40. To obtain t h i s r e s u l t a t o t a l c a m e r a
I A E A - S M R - 1 2 / 3 2 , 35 3 4 9
6.6 p s
(a)
FIG. 4 0 . M i c r o d e n s i t o m e t e r t r a c e of t h e pulses s h o w i n g ; (a) c o m p l e t e r e s o l u t i o n of c e n t r a l p a i r of p u l s e s

s e p a r a t e d by 6 . 6 ps; a n d (b) s u b - p u l s e r e v e a l e d as d o u b l e pulse s e p a r a t e d by 2. 5 ps, w i t h r e c o r d e d c l e a r
r e s o l u t i o n of < 2. 0 ps.
i n s t r u m e n t a l r e s o l u t i o n l i m i t of < 2 p s i s n e e d e d . Since t h e d y n a m i c s p a t i a l
r e s o l u t i o n (5 i p / m m at 1.1 x 10 10 c m - s" 1 ) l i m i t w a s 1.8 ps t h e t i m e
d i s p e r s i o n limit was < 1 ps as expected.
M o r e r e c e n t l y B a s o v et a l . [85] and F a n c h e n k o and F r o l o v [86] h a v e
e m p l o y e d t h e newly d e v e l o p e d " p i c o c h r o n " t i m e - r e s o l u t i o n i m a g e - c o n v e r t e r s
to study t h e p i c o s e c o n d s t r u c t u r e of m o d e - l o c k e d n e o d y m i u m l a s e r s .
E a r l i e r s t u d i e s of t h i s l a s e r with R u s s i a n i m a g e - t u b e c a m e r a s had b e e n
l i m i t e d t o a t i m e - r e s o l u t i o n of 20 p s [87, 88] . An e l e c t r i c f i e l d s t r e n g t h
of up t o 6 kV- c m ^ a t t h e p h o t o c a t h o d e i s o b t a i n e d in t h e " p i c o c h r o n "
i m a g e - t u b e by e m p l o y i n g a n e l e c t r o s t a t i c l e n s . An X - b a n d r e s o n a n c e c a v i t y
d e f l e c t i n g s y s t e m c o n t i n u o u s l y s w e e p s a p o i n t i m a g e a l o n g an e l l i p t i c a l p a t h
on t h e t u b e p h o s p h o r . A l i n e a r v o l t a g e r a m p of d u r a t i o n 30 n s , g e n e r a t e d
by a l a s e r - t r i g g e r e d s p a r k g a p , c a n a l s o be u s e d t o d e f l e c t t h e i m a g e
l i n e a r l y . A. f i v e - s t a g e i m a g e i n t e n s i f i e r f o l l o w e d t h e s t r e a k i m a g e - t u b e .
An o p t i c a l d e l a y l i n e w a s u s e d t o p r o d u c e s i m u l t a n e o u s r e c o r d i n g in two
o r m o r e c h a n n e l s . W h i l e t h e w r i t i n g s p e e d (4.5 - 6 x 10 1 0 cm-s" 1 ) and s p a t i a l
r e s o l u t i o n (5 i p / m m ) give a v a l u e Дт 5 = 5 x 1 0 " 1 3 s t h e 6 kV • cm* p h o t o -
c a t h o d e e x t r a c t i o n f i e l d g i v e s AT d = 2.2 x 10" 12 s [76] f o r l i g h t of w a v e -
l e n g t h 1.06 м т s o p h o t o e l e c t r o n t r a n s i t t i m e s p r e a d l i m i t s t h e c a m e r a
r e s o l u t i o n t o > 2 p s . The long t o t a l r e c o r d i n g t i m e of 1 5 - 2 0 n s s i m p l i f i e s
s w e e p t i m i n g and c a l i b r a t i o n p r o b l e m s but t h e u s e of a point i m a g e i n s t e a d
of a s l i t i m a g e i n c r e a s e s t h e d i f f i c u l t y with m i c r o d e n s i t o m e t r y . L e s s t o t a l
i n f o r m a t i o n i s o b t a i n e d and t h e r e s u l t i n g i n c r e a s e in s i g n a l f l u c t u a t i o n s
d e c r e a s e s the a c c u r a c y of m e a s u r e m e n t [85, 86] . The f a c i l i t y f o r p i c o -
second t i m e - r e s o l v e d spectroscopy i s also obviously lost. The a v e r a g e
d i s t a n c e b e t w e e n t h e m a x i m a of t h e p u l s e s t r u c t u r e w a s m e a s u r e d to be
2 . 5 p s [86] , in good a g r e e m e n t with t h e e x p e c t e d c a m e r a t i m e - r e s o l u t i o n
l i m i t . P r o v i d e d t h e n u m b e r of p h o t o e l e c t r o n s N f r o m t h e s p a t i a l r e s o l u t i o n
e l e m e n t ( ~ 0 . 2 m m ) of t h e input p h o t o c a t h o d e w a s < 1 0 0 , s a t u r a t i o n e f f e c t s
did not o c c u r and t h e r a n g e of u s e f u l o p e r a t i o n w a s 10 < N < 100. S i m i l a r
t i m e - r e s o l u t i o n w i t h a s l i t - i m a g e s t r e a k c a m e r a h a s a l s o been r e c e n t l y
a c h i e v e d by a n o t h e r R u s s i a n g r o u p [89] . T h u s t h e p r e s e n t l y a v a i l a b l e
i n s t r u m e n t a l t i m e - r e s o l u t i o n l i m i t o b t a i n a b l e with i m a g e - t u b e s t r e a k
3 5 0 BRADLEY
c a m e r a s i s s t i l l s e t by p h o t o e l e c t r o n t r a n s i t t i m e s p r e a d . While a t i m e -
r e s o l u t i o n < 1 ps c a r be obtained with dye l a s e r s o p e r a t i n g at w a v e l e n g t h s
n e a r the photocathode c u t - o f f 2 , t i m e r e s o l f t t i o n < 2 ps can only be a c h i e v e d
f o r N d : g l a s s p u l s e s by i n c r e a s i n g t h e e x t r a c t i o n f i e l d s t r e n g t h . The r e q u i r e d
field of 13 ООО V- cm" 1 should be f a i r l y e a s i l y p r o d u c e d with the f i n e m e s h
e x t r a c t i o n e l e c t r o d e d e s i g n of s t r e a k i m a g e - t u b e [ 7 8 ] .
30 psec
if i
FIG.41. O s c i l l o g r a m of m o d e - l o c k e d Nd: g l a s s l a s e r pulse t r a i n (6 ns pulse s e p a r a t i o n ) and s t r e a k p h o t o g r a p h
of s e c o n d h a r m o n i c of a " s i n g l e p u l s e " s h o w i n g p i c o s e c o n d s u b - s t r u c t u r e w i t h s e p a r a t i o n of 30 ps.
1. 9. Detection of s a t e l l i t e p u l s e s and s u b - s t r u c t u r e f r o m s t r e a k - c a m e r a
measurements
E a r l y m e a s u r e m e n t s [87] of N d : g l a s s l a s e r p u l s e s t r u c t u r e s , with a
s t r e a k c a m e r a t i m e r e s o l u t i o n of ~ 2 0 p s , showed m u l t i p l e s t r u c t u r e s p r e a d
o v e r h u n d r e d s of p i c o s e c o n d s , when T P F m e a s u r e m e n t s a p p a r e n t l y
!
W i t h a CSjSb p h o t o c a t h o d e a n d a C r e s y l - v i o l e t m o d e - l o c k e d d y e l a s e r [ 4 3 ] t u n e d t o n e a r the c u t - o f f
w a v e l e n g t h ( ~ 6 5 0 n m ) t h e r e s o l u t i o n l i m i t of 0 . 5 ps set by s p a t i a l r e s o l u t i o n and s t r e a k i n g speed a t t a i n a b l e
w i t h p r e s e n t s y s t e m s w o u l d b e a c h i e v e d a n d p u l s e s u b - s t r u c t u r e of t h e d u r a t i o n c o u l d be d i r e c t l y r e c o r d e d .
I A E A - S M R - 1 2 / 3 2 , 35 3 5 1
FIG.42. TOP O s c i l l o g r a m of m o d e - l o c k e d pulse t r a i n of R h o d a m i n e 6G d y e l a s e r o p e r a t i n g a t 6 0 5 n m .

T i m e s c a l e 50 n s / m a j o r d i v i s i o n .
BOTTOM S t r e a k p h o t o g r a p h of pulse 2 0 ns f r o m s t a r t . O v e r a l l d u r a t i o n of s t r e a k = 150 p s .
Dye l a s e r
FIG.43. M e t h o d of m e a s u r i n g pulse s h a p e s a t t w o d i f f e r e n t t i m e s a l o n g the s a m e pulse t r a i n . T h e pulse

d e l a y c a n b e v a r i e d t o study c h a n g e s in pulse p r o f i l e s a f t e r d i f f e r e n t n u m b e r s of passes t h r o u g h t h e l a s e r
cavity.
352 BRADLEY
gave p u l s e d u r a t i o n s of ~2 p s . L a t e r m e a s u r e m e n t s with the s a m e c a m e r a

s y s t e m [88] showed that p u l s e s n e a r the s t a r t of the t r a i n w e r e of s h o r t e r
d u r a t i o n and had l e s s s u b - s t r u c t u r e than t h o s e l a t e r in the p u l s e t r a i n .
The l a s e r s s t u d i e d in t h e s e i n v e s t i g a t i o n s e m p l o y e d a s a t u r a b l e a b s o r b e r
dye c e l l p l a c e d at a d i s t a n c e f r o m the m a x i m u m r e f l e c t i v i t y l a s e r m i r r o r
and s a t e l l i t e p u l s e s a r e e x p e c t e d in t h i s c o n f i g u r a t i o n and have been
p h o t o g r a p h e d d i r e c t l y with a K e r r - c e l l c a m e r a [52] . The f i r s t s t u d i e s
with t i m e r e s o l u t i o n ~ 5 ps [84] showed t h a t t h e p u l s e t r a i n f r o m a N d : g l a s s
l a s e r with an o p t i c a l l y c o n t a c t e d dye c e l l r a r e l y contained s a t e l l i t e s .
However, p u l s e s of even a p p a r e n t l y w e l l m o d e - l o c k e d t r a i n s could o c c a -
s i o n a l l y contain e x t r a p u l s e s and the d a n g e r of r e l y i n g on o s c i l l o s c o p e
t r a c e s f o r d i a g n o s i s i s c l e a r l y shown in F i g . 41. M e a s u r e m e n t s with a
~2 p s r e s o l u t i o n on both r i n g [85] and n o r m a l r e s o n a t o r [86] o s c i l l a t o r s
c o n f i r m e d t h a t the s h o r t e s t - d u r a t i o n p u l s e s o c c u r r e d in the i n i t i a l p a r t of
the t r a i n , 2 0 0 - 3 0 0 n s b e f o r e the giant p u l s e i n t e n s i t y m a x i m u m . L a t e r in
t h e t r a i n t h e p u l s e s w e r e s e e n to lengthen and d e v e l o p an i n c r e a s i n g l y
c o m p l e x s t r u c t u r e , with c o m p o n e n t s of a few p i c o s e c o n d s d u r a t i o n . Short
p u l s e s of d u r a t i o n < 1 0 ps a p p e a r only in the i n i t i a l p a r t of the t r a i n while
at t h e t r a i n m a x i m u m p u l s e s up to ~ 1 0 0 p s d u r a t i o n w e r e r e c o r d e d .
I n c r e a s i n g the s a t u r a b l e a b s o r b e r c e l l low l e v e l t r a n s m i s s i o n to 80% gave
s h o r t e r p u l s e s m o r e c o n s i s t e n t l y and t h e s h o r t e s t p u l s e o b s e r v e d (5 ps)
w a s o b t a i n e d with t h i s h i g h e r t r a n s m i s s i o n v a l u e s . The s i z e of t h e l a s e r
i n t r a - c a v i t y a p e r t u r e did not s e e m to be s i g n i f i c a n t but o p e r a t i n g j u s t above
Time
8 Round trips
(1 ) (2 )
FIG.44. M i c r o d e n s i t o m e t e r t r a c e s of s t r e a k p h o t o g r a p h s of p u l s e s f r o m 6 0 5 n m R h o d a m i n e 6G d y e l a s e r
a f t e r 8 round trips a n d 10 round trips f r o m t h e start of t h e p u l s e t r a i n .
365
IAEA-SMR-12/44,46,48
t h r e s h o l d w a s i m p o r t a n t f o r r e p r o d u c i b i l i t y a s found by o t h e r a u t h o r s
[44, 90] . T h e s e d i r e c t s t r e a k - c a m e r a m e a s u r e m e n t s c o n f i r m and c l a r i f y
e a r l i e r r e s u l t s obtained using intensity a u t o - c o r r e l a t i o n techniques
[83, 44, 51, 61] and K e r r - c e l l s h u t t e r s [52] .
T h e t e m p o r a l b u i l d - u p of m o d e - l o c k i n g h a s a l s o b e e n s t u d i e d [93] in
t u n a b l e dye l a s e r s a s a f u n c t i o n of t h e o p e r a t i n g w a v e l e n g t h . A P o c k e l ' s
c e l l s h u t t e r s e l e c t e d p u l s e s out of d i f f e r e n t p a r t s of t h e p u l s e t r a i n s .
W h e n a R h o d a m i n e 6G l a s e r w a s t u n e d [43] to o p e r a t e at 605 n m t h e r e
w a s a v e r y r a p i d b u i l d - u p of m o d e - l o c k i n g and s t r e a k s s u c h a s s h o w n in
F i g . 42 t h a t p u l s e s o c c u r r i n g w i t h i n a few r o u n d t r i p s (20 n s ) f r o m t h e s t a r t
of l a s e r a c t i o n h a v e d u r a t i o n s of ~ 1 0 0 ps and a r e c o m p o s e d of s e v e r a l
c o m p o n e n t s of s h o r t d u r a t i o n . T h e r a p i d s h o r t e n i n g of p u l s e d u r a t i o n at
t h i s w a v e l e n g t h can be s e e n in t h e m i c r o d e n s i t o m e t e r t r a c e s of F i g . 44
o b t a i n e d w i t h t h e e x p e r i m e n t a l a r r a n g e m e n t [91] of F i g . 4 3 . T h e s e t r a c e s
c l e a r l y s h o w t h e s e l e c t i o n of a s i n g l e s t r u c t u r e c o m p o n e n t a f t e r only two
r o u n d t r i p s t h r o u g h t h e d y e - l a s e r o s c i l l a t o r . It i s n o t i c e a b l e t h a t p u l s e
s t r u c t u r e i s a t t e n u a t e d at both t h e f r o n t and r e a r of t h e o v e r a l l p u l s e
TIME
(e)
300nsec
(d)
2 5 0 nsec
FIG.45. S t r e a k s s h o w i n g t i m e d e v e l o p m e n t w i t h i n pulse t r a i n f r o m R h o d a m i n e 6G d y e l a s e r o p e r a t i n g a t
612 n m . T i m e s shown a r e m e a s u r e d f r o m s t a r t of pulse t r a i n .
354 BRADLEY
I M ! I l
li И
F I G . 4 6 . Consecutive streaks of single dye laser pulses. Parallel plate reflectors were e m p l o y e d in the
o p t i c a l delay line to g e n e r a t e sub-pulses f r o m e a c h laser pulse with alternate separations of 60 ps and 190 ps.
Nore dle reproducibility of c a m e r a streaks (trigger jitter - 1 9 0 ps) and the absence of background. T i m e
resolution of c a m e r a <2 ps.
envelope, to be expected f r o m both non-linear absorption and saturable

amplification which occur in the quasi-continuous mode-locked dye l a s e r
[92] . When the l a s e r is tuned to longer wavelengths, pulse build-up time
takes longer [63] and microdensitometer t r a c e s of the streaked output at
different times [91] clearly illustrate (Fig. 45) the time-development of
the u l t r a s h o r t pulses. Initial random fluctuations superimposed on an
intense background evolve into broad pulse envelopes with superimposed
s u b - s t r u c t u r e . These pulses then shorten into an a s y m m e t r i c profile,
s t e e p e r at the leading edge, ujitil finally the pulse is reduced to a single
short component. These experimental r e s u l t s can be explained in t e r m s
of the photochemistry of the mode-locking [91]. Measurements of the
background energy content of dye l a s e r pulse t r a i n s showed that the signal-
to-background ratio was < 104 with l e s s than 3% of the total energy outside
I A E A - S M R - 1 2 / 3 2 , 35 3 5 5
the u l t r a s h o r t p u l s e s [81, 93] . The s t r e a k s of F i g . 46 d e m o n s t r a t e both

the a b s e n c e of b a c k g r o u n d and the e x c e l l e n t r e p r o d u c i b i l i t y obtainable with
t h e c a m e r a and the m o d e - l o c k e d dye l a s e r .
1. 10. M e a s u r e m e n t of CW m o d e - l o c k e d dye l a s e r s
The u s e of h i g h - g a i n i m a g e i n t e n s i f i c a t i o n in p i c o s e c o n d s t r e a k c a m e r a s ,
n e c e s s a r y to avoid s a t u r a t i o n and s p a c e c h a r g e e f f e c t s in the s t r e a k i m a g e
tube s e c t i o n [94] , m e a n s that v e r y low p o w e r p u l s e s can be s t u d i e d . With
the m e s h e x t r a c t i o n e l e c t r o d e tube a s p a t i a l r e s o l u t i o n e l e m e n t of 0.2 m m
on the tube p h o s p h o r c o r r e s p o n d s to a r e s o l u t i o n e l e m e n t of 0.06 m m at
the photocathode [95] . A s s u m i n g a q u a n t u m e f f i c i e n c y of 5 x 10" 3 at the
dye l a s e r w a v e l e n g t h f o r an S20 p h o t o c a t h o d e , the r e q u i r e d light p o w e r
d e n s i t y at the photocathode i s only 6 x 10" 15 J p e r r e s o l u t i o n e l e m e n t f o r a
s i g n a l - t o - n o i s e r a t i o of 10:1. The CW p a s s i v e l y m o d e - l o c k e d dye l a s e r
of p e a k p o w e r ~ 1 0 0 W and e n e r g y p e r p u l s e of 5 x 10" 10 J [ 32, 33, 66]
o p e r a t e s in a clean T E M 0 0 m o d e and can be e a s i l y f o c u s s e d down to the
60-/um cathode r e s o l u t i o n e l e m e n t , and thus d i r e c t m e a s u r e m e n t of p i c o -
s e c o n d p u l s e d u r a t i o n s with t h e l a s e r i s r e a d i l y a c h i e v e d . Two output
t r a i n s of p u l s e s e a c h of peak p o w e r ~ 0 . 5 W w e r e obtained by tilting the
tuning p r i s m slightly away f r o m t h e B r e w s t e r angle (Fig. 34). One of t h e s e
output b e a m s was u s e d f o r continuous m o n i t o r i n g of the s p e c t r a l and
t e m p o r a l b e h a v i o u r of the l a s e r . The u s u a l o p t i c a l delay line s y s t e m
[81, 94, 95] w a s e m p l o y e d to divide e a c h p u l s e in the s e c o n d t r a i n into two
p u l s e s s e p a r a t e d by 90 p s . P a i r s of p u l s e s w e r e f o c u s s e d with a 7.5 cm
c y l i n d r i c a l l e n s and so s p r e a d along the s t r e a k i n g s l i t , with the i m a g e s
FIG.47. S t r e a k c a m e r a m i c r o d e n s i t o m e t e r t r a c e of m o d e - l o c k e d d y e l a s e r p u l s e s .
3 5 6 BRADLEY
d i s p l a c e d r e l a t i v e l y . High d e n s i t y t r a c k s s u i t a b l e f o r m i c r o d e n s i t o m e t r y
w e r e e a s i l y obtained with the S20 p h o t o c a t h o d e i m a g e - t u b e e m p l o y e d . 3
The s t r e a k r e c o r d s showed t h a t the l a s e r output c o n s i s t e d of a c o n t i n u o u s
t r a i n of i s o l a t e d p i c o s e c o n d p u l s e s s e p a r a t e d by the 8 - n s r o u n d - t r i p t i m e of
the l a s e r r e s o n a t o r . C o r r e l a t i o n m e a s u r e m e n t s using s e c o n d - h a r m o n i c
g e n e r a t i o n (66] could give e r r o n e o u s r e s u l t s in this r e s p e c t s i n c e weak but
long l a s t i n g s a t e l l i t e p u l s e s could not be d e t e c t e d . The s h o r t e s t p u l s e
d u r a t i o n m e a s u r e d with the s t r e a k - c a m e r a w a s 4.7 ps ( F i g . 47). The s t r e a k
c a m e r a m a d e it r e l a t i v e l y e a s y to o p t i m i z e the CW l a s e r m o d e - l o c k i n g ,
p a r t i c u l a r l y to e n s u r e t h a t s a t e l l i t e p u l s e s w e r e e l i m i n a t e d .
The i n v e s t i g a t i o n s c a r r i e d out to date with e l e c t r o n - o p t i c a l s t r e a k
c a m e r a s have shown t h a t dye l a s e r p u l s e d u r a t i o n s a s s h o r t a s 1 p i c o s e c o n d
can be d i r e c t l y m e a s u r e d . P r e l i m i n a r y m e a s u r e m e n t s [96] with a m e s h
tube with an SI photocathode ( I n s t r u m e n t Technology L t d . ) have shown that a
1
M a n u f a c t u r e d by I n s t r u m e n t T e c h n o l o g y L t d .
I A E A - S M R - 1 2 / 3 2 , 35 357
p h o t o c a t h o d e e x t r a c t i o n f i e l d up to 20 000 V- c m " 1 can be a c h i e v e d c o r r e -

s p o n d i n g to a t i m e r e s o l u t i o n l i m i t of ~ 0 . 5 p s f o r m e a s u r e m e n t s of Nd : g l a s s
l a s e r p u l s e s . P u l s e s f r o m a m o d e - l o c k e d n e o d y m i u m l a s e r have been
m e a s u r e d d i r e c t l y and a t i m e - r e s o l u t i o n of < 5 ps obtained ( F i g . 48). T h u s
p u l s e d u r a t i o n m e a s u r e m e n t s and t i m e - r e s o l v e d s p e c t r o s c o p y with t h i s
t i m e - r e s o l u t i o n i s now p o s s i b l e in t h e v i s i b l e and n e a r i n f r a - r e d s p e c t r a l
regions.
2. S E L E C T I V E EXCITATION S P E C T R O S C O P Y
O r g a n i c dye l a s e r s w e r e f i r s t e m p l o y e d a s t u n a b l e f r e q u e n c y light
s o u r c e s f o r n a n o s e c o n d s p e c t r o s c o p y in the d i r e c t s p e c t r o g r a p h i c d e t e c t i o n
of o p t i c a l f r e q u e n c y S t a r k e f f e c t s [8] . In t h e s e e x p e r i m e n t s , the b r o a d b a n d
output of a dye l a s e r w a s u s e d to p r o v i d e a s y n c h r o n i z e d b a c k g r o u n d
continuum f o r m e a s u r e m e n t s of n e a r - r e s o n a n t o p t i c a l - f r e q u e n c y S t a r k
s h i f t s in p o t a s s i u m a b s o r p t i o n l i n e s . When a b s o r p t i o n l i n e s do not o r i g i n a t e
f r o m t h e ground s t á t e it i s n e c e s s a r y to s e l e c t i v e l y e x c i t e the bottom l e v e l
of t h e t r a n s i t i o n and p u l s e d f r e q u e n c y - t u n a b l e n a r r o w - b a n d dye l a s e r s [6, 7]
have p r o v e d e x c e l l e n t f o r t h i s a l s o . Thus by m e a n s of t h i s l a s e r p u m p e d
s e l e c t i v e e x c i t a t i o n it i s p o s s i b l e to p r e p a r e a t o m s in w e l l - d e f i n e d s t a t e s
f o r d i r e c t m e a s u r e m e n t s of a t o m i c l e v e l l i f e t i m e s and c r o s s - s e c t i o n s , and
f o r t h e d e t e c t i o n of h i g h e r t e r m s of s e r i e s and a u t o i o n i z a t i o n l e v e l s not
r e a c h e d f r o m the ground state. Likewise resonant coherent interactions
such a s s e l f - i n d u c e d t r a n s p a r e n c y and l i n e a r d i s p e r s i o n d e l a y s can be
i n v e s t i g a t e d [97] .
T h e h i g h - e n e r g y , h i g h - p o w e r p u l s e s o b t a i n a b l e f r o m dye l a s e r s ,
p u m p e d by p o w e r f u l f l a s h l a m p s [9, 41, 98] o r by g i a n t - p u l s e s o l i d - s t a t e
l a s e r s and t h e i r h a r m o n i c f r e q u e n c i e s [3, 4, 9] have been e m p l o y e d f o r
t h e s e l e c t i v e e x c i t a t i o n of t r i p l e t c a l c i u m [99] , doublet p o t a s s i u m [100]
and s i n g l e t m a g n e s i u m [101] a t o m i c l e v e l s . P r e v i o u s o b s e r v a t i o n s of
a b s o r p t i o n f r o m e x c i t e d l e v e l s of a t o m i c m e t a l v a p o u r s had been f r o m low
lying l e v e l s , t h e r m a l l y populated at n o r m a l oven t e m p e r a t u r e s , o r f r o m
l o w e r m e t a s t a b l e l e v e l s e x c i t e d in shock t u b e s [102] . With dye l a s e r s
s e l e c t e d h i g h e r l e v e l s can be s u b s t a n t i a l l y populated and s t i m u l a t e d
e l e c t r o n i c R a m a n s c a t t e r i n g [103] and photoionization [101, 104, 105] f r o m
p o t a s s i u m and r u b i d i u m have been d e t e c t e d e x p e r i m e n t a l l y . A b s o r p t i o n
s p e c t r a a r e n o r m a l l y e m p l o y e d f o r t h e d e t e c t i o n of h i g h e r s e r i e s m e m b e r s
and a u t o i o n i z a t i o n l e v e l s , and the capability of obtaining in a b s o r p t i o n
t r a n s i t i o n s to l e v e l s not r e a c h e d f r o m the ground s t a t e g r e a t l y e x t e n d s t h e
study of s e r i e s p e r t u r b a t i o n s and a u t o i o n i z a t i o n . T h e r e i s the i m p o r t a n t
added p r a c t i c a l a d v a n t a g e t h a t l e v e l s above the n o r m a l i o n i z a t i o n l i m i t can
be t h u s i n v e s t i g a t e d without w o r k i n g in the e x p e r i m e n t a l l y d i f f i c u l t v a c u u m -
ultra-violet s p e c t r a l region, since absorption takes place f r o m levels well
above t h e ground s t a t e . As e x a m p l e s of the u s e of t h i s new t e c h n i q u e of
s e l e c t i v e e x c i t a t i o n s p e c t r o s c o p y , t h e e x p e r i m e n t s on s e l e c t i v e population
of r u b i d i u m and p o t a s s i u m [100] and r e s o n a n t - R a m a n s c a t t e r i n g f r o m t h e s e
l e v e l s [103] will be d e s c r i b e d , t o g e t h e r with s o m e r e c e n t s t u d i e s [106] of
s e r i e s p e r t u r b a t i o n s and a u t o i o n i z a t i o n l e v e l s in Ba I and Mg I.
358 BRADLEY
в — ь
Oye Laser 1
Dye Laser 2
To
• \ • Spectrograph
Giant Pulse Rubidium

Cell
Ruby Laser
Pump
FIG.49. D o u b l e d y e l a s e r p u m p e d by g i a n t pulse ruby l a s e r f o r s e l e c t i v e e x c i t a t i o n of a l k a l i v a p o u r s .
2.1. S e l e c t i v e e x c i t a t i o n of r u b i d i u m
The e x p e r i m e n t a l a r r a n g e m e n t f o r t h e s e l e c t i v e e x c i t a t i o n of the
5 2 P 3 /2 l e v e l of r u b i d i u m i s s h o w n in F i g . 49. A 40 MW, 40 n s g i a n t - p u l s e
r u b y l a s e r p u m p e d s i m u l t a n e o u s l y , by m e a n s of a b e a m s p l i t t e r , two tuned
dye l a s e r s . L o n g i t u d i n a l p u m p i n g of t h e 10" 4 M s o l u t i o n of 33 1 d i m e t h y l 22 1
o x a t r i c a r b o c y a n i n e i o d i d e , w a s a c h i e v e d by m e a n s of t h e p r i s m a r r a n g e m e n t s
shown. A 300 l i n e s / m m e c h e l l e cavity r e f l e c t o r , m o u n t e d in a u t o c o l l i m a t i o n
c l o s e to t h e b l a z e a n g l e of 63°,. p r o d u c e d f r o m t h e f i r s t dye l a s e r a 30 n s ,
100 kW p u l s e with a 1 c m " 1 wide s p e c t r u m , f r e q u e n c y t u n a b l e a r o u n d 780 n m ,
by r o t a t i o n of t h e e c h e l l e m o u n t i n g . In t h e s e c o n d l a s e r t h e e c h e l l e g r a t i n g
r e f l e c t o r w a s u s e d at 31° a n g l e of i n c i d e n c e to p r o d u c e a b r o a d e r output
s p e c t r u m . The 1 n m w i d e s p e c t r u m of t h i s l a s e r w a s an e f f e c t i v e l y
s t r u c t u r e l e s s c o n t i n u u m , s o f a r a s t h e r e s o l u t i o n of t h e 3 - m e t r e s p e c t r o -
- 9 - 1 /°
graph (resolution 3 x 1 0 c m , 3 nm/A d i s p e r s i o n ) . By a d d i n g a F a b r y -
P e r o t i n t e r f e r o m e t e r to t h e f i r s t l a s e r t h e output s p e c t r u m could be f u r t h e r
n a r r o w e d t o 10" 1 cm" 1 . The n a r r o w - b a n d l a s e r output w a s u s e d f o r
r e s o n a n c e p u m p i n g of the 5S-,y2-> 5 2 P 3 / 2 t r a n s i t i o n (X 780 n m ) and t h e b a c k g r o u n d
continuum f r o m the second l a s e r for simultaneously r e c o r d i n g the u p p e r -
s t a t e a b s o r p t i o n l i n e s 5 2 P 3 / 2 - 5 2 D g / 2 , ^ D ^ i X 775.8 n m , 776 n m ) . The
l i f e t i m e of t h e 5 2 I ^ / 2 l e v e l i s ~ 3 0 ns and t h a t of t h e 5 2 D 3 / 2 l e v e l i s ~ 1 m s .
A r u b i d i u m c e l l t e m p e r a t u r e of 370°K gave an a t o m d e n s i t y of ~ 3 x 10 1 2 cm" 3 .
H e l i u m at a p r e s s u r e of 100 t o r r was u s e d a s a b u f f e r g a s to r e m o v e t h e
p o s s i b i l i t y of any n o n l i n e a r c o h e r e n t p u l s e i n t e r a c t i o n s . T h e 5 S ^ g t o
5 2 P 3 / 2 t r a n s i t i o n w a s e a s i l y s a t u r a t e d by t h e 100 kW l a s e r p u m p , and t h e
&2p 5 2
3/2 ° 3 / 2 t r a n s i t i o n s at X 775.8 n m and Л 776 n m w e r e c l e a r l y
r e c o r d e d in a b s o r p t i o n [100] .
2.2. S t i m u l a t e d S t o k e s and a n t i - S t o k ë s e l e c t r o n i c R a m a n s c a t t e r i n g
T h e s u c c e s s i v e p r o c e s s e s involved in s t i m u l a t e d s c a t t e r i n g f r o m
p o t a s s i u m a r e s h o w n in F i g . 50. While s t i m u l a t e d R a m a n - S t o k e s [107] and
a n t i - S t o k e s [108] s c a t t e r i n g h a d been r e p o r t e d , t h e s i m u l t a n e o u s
g e n e r a t i o n of both l o w e r and h i g h e r f r e q u e n c y c o m p o n e n t s and t h e i r o v e r t o n e s
1 A E A - S M R - 1 2 / 3 1 . 32 3 5 9
I.
U рз/2 •
и Р'/2 •
VL V ASI VL VASn VAS] VSI VL VSn VSI

.1
Д
is ''2 -i
Û "T
2Д
"1
lb) ( с ) (d) (e)
FIG.50. S t i m u l a t e d R a m a n processes in p o t a s s i u m v a p o u r .
F I G . 51. M i c r o d e n s i t o m e ter t r a c e of s t i m u l a t e d e l e c t r o n i c R a m a n s c a t t e r i n g in s e l e c t i v e l y e x c i t e d p o t a s s i u m
s h o w i n g b o t h S t o k e s and a n t i - S t o k e s c o m p o n e n t s a n d t h e i r o v e r t o n e s .
360 BRADLEY
was e a s i l y o b t a i n e d [103] with a high-power t u n a b l e dye l a s e r . The 4 2 P 3 / 2

l e v e l w a s s e l e c t i v e l y e x c i t e d by a 10" 4 M solution in p y r i d i n e of I I 1
d i e t h y l - y - c y a n o 221 d i c a r b o c y a n i n e t e t r a f l u o r o b o r a t e dye l a s e r , pumped
by a giant p u l s e r u b y l a s e r and tuned f o r r e s o n a n c e p u m p i n g of the
4 S 1 / 2 - 4 2 P 3 / 2 t r a n s i t i o n {v h = 13 043 cm" 1 ). The dye l a s e r b e a m , of peak
p o w e r 1 MW cm" 2 , in a 40 n s p u l s e of 2 cm" 1 band width, p u m p e d a 6 c m
long p o t a s s i u m c e l l . The output light f r o m the c e l l , in the f o r w a r d d i r e c t i o n ,
w a s c o l l e c t e d by a l e n s , f o c u s s e d f o r p a r a l l e l i n c i d e n t light, on t h e s l i t of a
5 m e t r e s p e c t r o g r a p h . When t h e l a s e r f r e q u e n c y w a s tuned to within 8 c m " 1
of t h e 13 043 cm" 1 t r a n s i t i o n (X 766.49 n m ) , s t i m u l a t e d a n t i - S t o k e s s c a t t e r i n g
w a s o b s e r v e d at c e l l t e m p e r a t u r e s of ~240°C ( K - v a p o u r p r e s s u r e of
5 x 10" 2 T o r r ) . At a c e l l t e m p e r a t u r e of 280°C (2 x 10" 1 T o r r K - v a p o u r )
Stokes e m i s s i o n a l s o o c c u r r e d . As e x p e c t e d the a n t i - S t o k e s s c a t t e r i n g
f r o m t h e i n i t i a l l y populated 4 2 P y 2 w a s t h e s t r o n g e r of the two s c a t t e r e d
l i n e s , which w e r e both d i s p l a c e d f r o m t h e l a s e r b e a m f r e q u e n c y by t h e
57.7 c m " 1 e n e r g y d i f f e r e n c e of t h e p o t a s s i u m doublet. In the m i c r o d e n s i t o -
m e t e r t r a c e of F i g . 51 s e c o n d Stokes s c a t t e r i n g f r o m the 4Pjy 2 l e v e l i s c l e a r l y
s e e n . As e x p e c t e d f r o m t h i s s c a t t e r i n g r e s o n a n t p r o c e s s , f i r s t Stokes
s c a t t e r i n g i s n e a r l y as s t r o n g as the f i r s t a n t i - S t o k e s s c a t t e r i n g . The
s e c o n d a n t i - S t o k e s line i s w e a k e s t in i n t e n s i t y , being f u r t h e s t away f r o m
R a m a n r e s o n a n c e . When t h e l a s e r f r e q u e n c y w a s tuned t h r o u g h r e s o n a n c e
with t h e 13 043 c m " 1 t r a n s i t i o n , the s c a t t e r e d c o m p o n e n t s tuned with i t ,
m a i n t a i n i n g t h e i r c o n s t a n t s e p a r a t i o n s of 57.7 cm* 1 .
E m p l o y i n g a r u b i d i u m c e l l and a p o l y m e t h i n e dye l a s e r pumped by a
m o d e - l o c k e d r u b y l a s e r [97] to p r o d u c e a dye l a s e r t r a i n of 2 ns p u l s e s ,
e a c h s e p a r a t e d by 10 n s , tuned to r e s o n a n c e with t h e S S ^ - " 5 2 P x / 2 t r a n s i t i o n
(12 599 cm" 1 ) of r u b i d i u m , both Stokes and a n t i - S t o k e s l i n e s w e r e r e c o r d e d .
The l a s e r peak p o w e r w a s f o c u s s e d into the 7 c m long a l k a l i v a p o u r c e l l
to give a p e a k p o w e r of 280 MW • c m " 2 . T h e s p e c t r o g r a p h w a s e m p l o y e d a t
low d i s p e r s i o n (14° g r a t i n g angle) and a s l i t width of 2 m m gave a r e s o l u t i o n
of 10 cm" 1 . In addition to the n o r m a l s t i m u l a t e d R a m a n c o m p o n e n t s ,
s e p a r a t e d f r o m t h e l a s e r line by the 238 cm" 1 e n e r g y d i f f e r e n c e of the
52P^y2J 5 2 Pg^ 2 l e v e l s , s o m e t i m e s e x t r a R a m a n c o m p o n e n t s s h i f t e d by 213 cm" 1
only w e r e o b t a i n e d . S o m e t i m e s t h e s e c o m p o n e n t s w e r e r e c o r d e d alone
and s o m e t i m e s t o g e t h e r with t h e n o r m a l R a m a n l i n e s . T h e s e e x t r a
c o m p o n e n t s could a r i s e f r o m the p r e s e n c e of the h e l i u m ( p r e s s u r e 100 T o r r )
l e a d i n g to d i f f u s e a b s o r p t i o n bands [109] and s c a t t e r i n g f r o m t h e wings of
these lines.
2. 3. Ba I s p e c t r a
F i g u r e 52 s h o w s a s i m p l i f i e d t e r m d i a g r a m of Ba I. To e q u a l i z e the
population d e n s i t i e s of t h e б э б р ^ l e v e l and the 6s 2 1 S 0 ground s t a t e r e q u i r e s
a high p o w e r l a s e r o p e r a t i n g at X 553.5 n m . The s a t u r a t i n g p o w e r d e n s i t y ,
Ps ; f o r a h o m o g e n e o u s l y b r o a d e n e d line m u s t s a t i s f y t h e condition
P s a 1 » h y / T 1 where i s the c r o s s - s e c t i o n f o r the 6 s 1 S 0 -* б р 1 ? ^
t r a n s i t i o n and T, i s t h e l i f e t i m e of the 6p 1 ^ s t a t e . F o r T j = 8 m s [111]
and Oj ~ 2 x 10" 1 2 c m 2 , P s » 25 W • cm" 2 , e a s i l y a c h i e v e d with a pulsed dye
l a s e r . To o b s e r v e a b s o r p t i o n to h i g h e r l e v e l s w i l l r e q u i r e an e x c i t e d
s t a t e population d e n s i t y of ~ 3 x 10 cm" 2 , a s s u m i n g an a b s o r p t i o n c r o s s -
s e c t i o n of 10" l 6 c m 2 . T h i s will then give an a b s o r p t i o n of ~95%. F o r an
oven long enough to a b s o r b a l l of the p u m p l a s e r b e a m the r e q u i r e d p o w e r
I A E A - S M R - 1 2 / 3 2 , 35 361
QUARTZ BEAM
PLATE EXPANDER
100-/.R
DYE MIRROR
CELL
/ i с р в о / а / д о
553-5 n m — Bo I
M E T A L VAPOUR FABRY-PEROT
OVEN ETALONS
265 n m
л
ci • о PELLICLE
AXICON
530 nm
DYE C E L L
FILTER
A D P Xdl
FILTER
EH S.H. of 1060 n m
SPECTROGRAPH
SPHERO -
.BEAM A D P Xol
CYLINDRICAL
SPLITTER F H . of 1060 n m LENS
1060 n m 1
(from Nd: GLASS LASER SYSTEM)
FIG. 53. Experimental arrangement for selective excitation of 6s 6p 1PJ level of Ba I.

362 BRADLEY
d e n s i t y f o r an e x c i t a t i o n d e n s i t y of N (cm" 2 ) i s P N ~ NÍIÍZ/T^ w h e r e r e s o n a n t
i m p r i s o n m e n t i s n e g l e c t e d . F o r the above Ba I t r a n s i t i o n , P N = 1.5 MW • cm" 2
f o r N = 3 x 10 16 c m . T h i s t u n a b l e p o w e r d e n s i t y in a t y p i c a l D o p p l e r width
can at p r e s e n t only be a c h i e v e d with l a s e r - p u m p e d dye l a s e r s . While
i d e a l l y the p u m p i n g l a s e r band width should m a t c h t h a t of the m e t a l t r a n s i t i o n ,
even if t h e r e i s s t r o n g p u m p i n g in the wings of the line p r o f i l e , by u s i n g
a high p r e s s u r e of b u f f e r gas in the oven any i n i t i a l n o n - M a x w e l l i a n
d i s t r i b u t i o n of e x c i t e d a t o m s w i l l be r a p i d l y r e m o v e d [ 1 1 2 ] .
The g e n e r a l e x p e r i m e n t a l a r r a n g e m e n t i s shown in F i g . 53. A single
t r a n s v e r s e mode Nd:glass oscillator, actively Q-switchedwith a Pockels
c e l l , and a m p l i f i e r s , p r o d u c e d a 10 J o u l e 30 ns p u l s e with a u n i f o r m
b e a m c r o s s - s e c t i o n . F r e q u e n c y - d o u b l e d in a p h a s e - m a t c h e d A D P c r y s t a l
p r o d u c e d a 1J, 30 ns p u l s e at X 530 n m . P a r t of the 530 nm b e a m , f i l t e r e d
f r o m the f u n d a m e n t a l f r e q u e n c y , t r a n s v e r s e l y p u m p e d the dye l a s e r c e l l
(2.5 x 10 _3 M s o l u t i o n of 2 1 7 1 d i c h l o r o f l u o r e s c e i n in e t h a n o l , with 1%
a m m o n i a ) which w a s 4 c m long, 1 cm 2 c r o s s - s e c t i o n and had 10° wedged
w i n d o w s . With two i n t r a c a v i t y F a b r y - P e r o t é t a l o n s , with 5 and 50 ijm g a p s , a
s p e c t r a l b a n d w i d t h < 0 . 1 nm and a 20 ns 60 m j p u l s e w e r e o b t a i n e d , giving
a p u m p p o w e r d e n s i t y of 30 MW- cm" 2 , in the 0.1 cm 2 b e a m . A p e l l i c l e
b e a m s p l i t t e r r e f l e c t e d 20% of the X 530 nm b e a m into a s e c o n d f r e q u e n c y
doubling A D P c r y s t a l , to g e n e r a t e the f o u r t h h a r m o n i c at X 265 n m . T h i s
u. v. b e a m e x c i t e d f l u o r e s c e n t d y e s in a s p e c i a l l y d e s i g n e d axicon c e l l to
produce background pulses. C o i n c i d e n c e to ± 1 ns of the dye l a s e r
p u l s e p u m p i n g t h e b a r i u m v a p o u r and the f l u o r e s c e n t b a c k g r o u n d continua
w a s a c h i e v e d by a d j u s t i n g the o p t i c a l path l e n g t h s .
A s i m p l e s t a i n l e s s s t e e l tube (2 c m i n t e r n a l d i a m e t e r and 35 c m long),
h e a t e d with a r e s i s t a n c e coil, c o n s t i t u t e d the b a r i u m v a p o u r oven, which
a l s o contained a r g o n gas at 100 T o r r as b u f f e r g a s . O p e r a t e d at 850° the
b a r i u m v a p o u r p r e s s u r e w a s 10 16 a t o m s - cm" 3 . A b s o r p t i o n s p e c t r a w e r e
r e c o r d e d with a r e s o l u t i o n of 0.02 n m . A s p e c t r a l r a n g e of 20 nm could be
p h o t o g r a p h e d at one t i m e , which w a s a l s o the t y p i c a l u s e f u l bandwidth of
the s c i n t i l l a t o r d y e s (Table II). Using Ilford HP 3 o r F P 4 p l a t e s up to
8 l a s e r p u l s e s w e r e r e q u i r e d to obtain an e x p o s u r e s u i t a b l e f o r m i c r o d e n s i t o -
metry.
T A B L E II. FLUORESCING DYES F O R CONTINUA
Concentration Range Lifetime

Dye Solvent
(molar, M) (nm) (ns)
Esculin monohydrate ethanol + lfo NH 3 4 x 10"4 442 - 475 2.2
Dimethyl POPOP ethanol 2 x 10"4 423 - 442 1.5
bis MSB ethanol 10"3 404 - 424 1.4

a BPO ethanol 10""3 385 - 408 2.3
PBD ethanol 10"3 363 - 382 1.1
PPD ethanol Iff"3 344 - 363 1.5
Para-terphenyl cyclohexane 10"3 330 - 350 1

B a l ABSORPTION SPECTRA LASER PUMPED 6S2 ' s 0 - б э б р ' Р , 0 crt 5 5 3 - 5 n m
24 21 6 s 6 p 'P, 0 - 6 s n d 'D 2
25
LIMIT
26
420 430 440 450 nm
f6s(n«1)sSо
0
" I 41 39 37 35 33
6s6p'p* • 36 39 3! 31 30 29 21
J "Vř
|6snd'02
6s6p'P, - 6s7d'Dj
A18 419 420 421 nm
FIG. 54. Absorption spectra 6s 6p 'pf - 6s nd 'D 2 series of Ba I showing series perturbation of 6s 6p ' p j -
6s nd *DJ, 6S 6p 'P? - 6s (n + l)s ' S j , by 5d 7d ' d 2 l e v e l .
364 BRADLEY
T A B L E III. 6s 6p !pO - 6s nd SERIES (IONIZATION LIMIT

23 972. 9 cm" 1 )
n X ( a i r ) nui J V (vacuum; cm n
*
9 469.911 21274.7 6.378

10 455.909 21937.7 7.344) ,
11 445.842 5d8S D
22423.2 8.417! 2
12 439.997 22721.0 9.363
13 435.661 22947.2 10.343
14 432.251 23128.2 11.398
15 429.900 23254.7 12.361
16 428.020 23356.8 13.346
17 426.517 23439.1 14.338
18 425.294 23506.5 15.339
19 424.299 23561.7 16.336
20 423.467 23607.9 17.339
21 422.772 23646.8 18.344
22 422.192 23679.2 19.330
23 421.688 23707.5 20.334
24 421.258 23731.7 21.330
25 420.880 23753.1 22.344
26 420.61 23768.4 23.16 ) .
) 5d7d D
27 420.21 23791.2 24.58 )
28 419.981 23803.9 25.48

29 419.763 23816.3 26.47
30 419.567 23827.4 27.46
31 419.394 23837.2 28.44
32 419.23 23846.4 29.45
33 419.09 23854.6 30.46
34 418.94 23862.9 31.59
35 418.83 23869.3 32.55
36 418.73 23875.1 33.50
37 418.63 23880.6 34.48
38 418.53 23886.5 35.64
39 418.45 23890.9 36.58
40 4.1.8.39 23891.6 37.44
IAEA-SMR-12/32, 35 365
T A B L E IV. 6s 6p - 6s(n + l ) s 1s0 SERIES
n X (air) nm v (vacuum) cm - 1 n¥
26 420.56 23 771.3 23.22
27 420.27 23 787.6 24.34
TABLE V. 6s 6p - 5d n s ^ SERIES (LIMIT 29 647. 7 cm"1)
n X (air) nm v (vacuum) cm"1 n*
8 451.067 22 163.4 3.83
9 402.81 24 818.6 4.77
10 380.63 26 264.6 5.70
11 367.17 ' 27 227.5 6.73
Tuning of t h e p u m p i n g dye l a s e r to r e s o n a n c e w a s checked by c o m p a r i n g

t h e l a s e r output s p e c t r u m with a r e s o n a n c e a b s o r p t i o n s p e c t r u m of t h e
b a r i u m v a p o u r . T y p i c a l s p e c t r a obtained a r e shown in F i g . 54 w h e r e the
two s e r i e s 6s 6p ^ - 6s nd 1 D 2 , 6s 6p - 5d n s 1 D 2 a r e i n d i c a t e d . T h e
6s 6p X P° - 6s nd 1 D 2 s e r i e s w e r e extended f r o m n = 9 to n = 41. Table III
l i s t s the m e a s u r e d w a v e l e n g t h s , t h e i r i d e n t i f i c a t i o n and the v a l u e of the
R y d b e r g d e n o m i n a t o r n* given by n* = \ l R / T n , w h e r e R i s the R y d b e r g c o n s t a n t
and T n i s t h e e n e r g y v a l u e of t h e nth t e r m m e a s u r e d f r o m t h e i o n i z a t i o n
l i m i t , u s i n g t h e v a l u e of G a r t o n and Codling. Only two l i n e s of the s e r i e s
6s б р ^ - 6s(n + IJSÍSQ w e r e p o s i t i v e l y i d e n t i f i e d . T a b l e III shows p e r -
t u r b a t i o n s in the q u a n t u m d e f e c t of t h e 6s 6p V i - 6 s nd 1 D 2 s e r i e s f o r
n = 26 and 27. T h e s e p e r t u r b a t i o n s , a r e c a u s e d by t h e 5d 7d "'Dj l e v e l , and
s h i f t s t h e two l i n e s s u f f i c i e n t l y to r e v e a l the n = 26 and n = 2 7 l i n e s of the
6s 6p - 6s(n + l J S ^ s e r i e s ( F i g . 54).
T a b l e IV shows t h a t , as e x p e c t e d , the l i n e s of the l a t t e r s e r i e s a r e not
p e r t u r b e d by the 5d 7d l e v e l , and f r o m F i g . 54 it can be s e e n that t h e two
s e r i e s a r e of c o m p a r a b l e i n t e n s i t i e s . A l s o r e c o r d e d w e r e t h e s e r i e s
б э б р ^ - 5 d n s D2 i n c l u d i n g the a u t o i o n i z a t i o n l i n e s c o r r e s p o n d i n g to
n = 9, 10, 11 l i s t e d in T a b l e V ( F i g . 55). F i g u r e 56 s h o w s t h e e x p e r i m e n t a l
a r r a n g e m e n t f o r the s e l e c t i v e e x c i t a t i o n of the 3s 3p ^-P® l e v e l of m a g n e s i u m I.
T h i s e m p l o y e d t h e t u n a b l e s e c o n d - h a r m o n i c f r e q u e n c y of a R h o d a m i n e 6G
dye l a s e r [28] a l r e a d y d e s c r i b e d . Tuning to r e s o n a n c e with the 3s 2 XS0 -
3s 3p '•pj t r a n s i t i o n (X 285.21 nm) the 0.04 n m b a n d - w i d t h - l a s e r m e g a w a t t
b e a m p r o v i d e d enough population of t h e u p p e r l e v e l to r e c o r d the a b s o r p t i o n
s p e c t r u m of F i g . 57. The s c i n t i l l a t o r dye p u m p e d by t h e 265 n m l a s e r b e a m
p r o v i d e d the b a c k g r o u n d a b s o r p t i o n c o n t i n u u m . The a b s o r p t i o n s e r i e s
3s З р 1 ? " ^ 3 s n d ! D 2 w a s d e t e c t e d up to n = 24 and t h i s e x t e n d s the s e r i e s
f r o m n = 13 p r e v i o u s l y o b s e r v e d in e m i s s i o n s p e c t r a [117] . F i g u r e 58
shows t h e indole f l u o r e s c e n c e c o n t i n u u m , with and without e x c i t e d m a g n e s i u m
Bal ABSORPTION SPECTRA Laser pumped 6 s 2 'S 0 - 6 s 6p'P? at 553-5 nm
Autoionization series 6 s 6 p 'p, 5 dns ' D2
370 380 390 400 nm
FIG.55. 6s 6p - 5d ns *D2 series for n = 9, 10, 11 autoionization lines of barium.

I A E A - S M R - 1 2 / 3 2 , 35 367
QUARTZ BEAM
PLATE EXPANDER
A D P X al 100V.R
S.H.G. Ol DYE MIRROR
DYE L A S E R CELL
S
/ • o c p » H H ř
2 8 5 . 2 n m — Mg I
METAL VAPOUR FABRY-PEROT
OVEN ETALONS
265 n m
e PELLICLE
AX ICON
530 n m j
DYE C E L L FILTER
SPECTROGRAPH
FILTER
Ш A D P Xal
S.H. of 1 0 6 0 n m
SPHERO-
BEAM ADP Xal С
CYLINDRICAL
SPLITTER F.H. of 1 0 6 0 n m LENS
1060 nm
(from Nd: GLASS LASER SYSTEM)
FIG. 56. Experimental arrangement for selective excitation of 3s 3p 1 pj level of Mg I.
Mg I Laser pumped 2 8 5 . 2 1 nm 3s' 50 — 3s3p'P,°
3 s 3 p 'P, - 3 s n d '0 2
23 21
24 I 22 I 20 19 18 17 16 15 14 13 12
H i l l I I I I I I I I
380 382 384 386 nm
FIG. 57. Higher terms of 3s Зр - 3s nd l D 2 absorption series of selectively excited Mg I. Triplet

absorption lines arising from ' p j - 3P0 crossing are also present.
3 6 8 BRADLEY
AUTOIONIZATION IN Mg I Laser pumped 3s2lS0 —

3s3p'R°
290 320 nm
Mg 1 3s Зр'Ч" — 3p2 'So ABSORPTION
о
о
290 300 310 320 nm
FIG . 5 8 . TOP Microdensitometry traces of the indole continuum with and without selective excitation of
the magnesium vapour.
BOTTOM Absorption profile of the 3s 3p 1P? - 3pz 'Sq transition.
in t h e o v e n , r e c o r d e d in f i r s t o r d e r w i t h a 200 д ю s l i t w i d t h . S t r o n g
a b s o r p t i o n at X 300.9 n m f r o m t h e a u t o i o n i z a t i o n t r a n s i t i o n 3s 3p -
3p 2 !So c a n be c l e a r l y s e e n n e a r t h e p e a k of t h e c o n t i n u u m . (In t h i s s p e c t r a l
r e g i o n t h e r e a r e v e r y few s u i t a b l e f l u o r e s c i n g d y e s and it i s not p o s s i b l e
to g e n e r a t e a b r o a d e r s p e c t r a l b a c k g r o u n d [ 1 1 4 ] . ) T h e r e i s good a g r e e m e n t
with t h e p r e d i c t e d r e s o n a n c e at X 297.7 n m [ 1 1 8 ] . By q u a n t i t a t i v e m i c r o -
d e n s i t o m e t r y a l i n e : w i d t h o f 3.5 n m (FWHM) w a s m e a s u r e d f r o m t h e
I A E A - S M R - 1 2 / 3 2 , 35 3 6 9
a b s o r p t i o n l i n e p r o f i l e of F i g . 58, obtained by s u b t r a c t i n g the n o r m a l i z e d

b a c k g r o u n d i n t e n s i t y p r o f i l e . A peak c r o s s - s e c t i o n of 5 x 10"16 c m 2 w a s
e s t i m a t e d f r o m t h e s p e c t r a l d e n s i t i e s and the excited s t a t e population
d e t e r m i n e d by the l a s e r flux. Both of t h e s e e x p e r i m e n t a l v a l u e s a r e in
e x c e l l e n t a g r e e m e n t with t h o s e c a l c u l a t e d . F i g u r e 58 a l s o shows two s e t s
of t r i p l e t e m i s s i o n m u l t i p l e t s . T h e s e l e c t i v e l y e x c i t i n g p u m p i n g b e a m at
X 285.2 n m will a l s o c a u s e ionization f r o m the 3s 3p s t a t e and r e c o m b i -
nation c a n l e a v e the a t o m in one of the e x c i t e d t r i p l e t s t a t e s . We have
r e c o r d e d e m i s s i o n l i n e s t e r m i n a t i n g in t h e 3s 3p 3 p° l e v e l f r o m 3s ns J S,
3s nd 3 D and 3p 2 3 P l e v e l s . When the a r g o n b u f f e r gas p r e s s u r e w a s
i n c r e a s e d to 600 T o r r f r o m the 300 T o r r p r e s s u r e n o r m a l l y u s e d t h e s e
e m i s s i o n l i n e s g e n e r a l l y d i s a p p e a r e d and often a p p e a r e d in a b s o r p t i o n .
This i n d i c a t e s that i n t e r - s y s t e m c r o s s i n g i s then o c c u r r i n g d u r i n g the
l i f e t i m e of the b a c k g r o u n d p u l s e .
C a l c u l a t i o n s [118] c a r r i e d out u s i n g a 1 D 2 c o n t i n u u m s t a t e a l s o gave
r e s o n a n c e s t r u c t u r e in the a b s o r p t i o n f r o m the 3s Зр l e v e l at w a v e l e n g t h s
l e s s than X 200 n m which could be i d e n t i f i e d a s 3p np 1 D f o r n ž 4. E x p e r i -
m e n t s a r e in p r o g r e s s to l o c a t e o t h e r r e s o n a n c e s and to m e a s u r e the
3s 3p - 3p 2 1 S 0 p h o t o i o n i z a t i o n c r o s s - s e c t i o n p h o t o e l e c t r i c a l l y with a
s e c o n d t u n a b l e dye l a s e r p r o b e .
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P A R T II: MOLECULES
IAEA-SMR-12/11
FOUNDATION OF THE THEORY

O F DIATOMIC M O L E C U L E S
I. KOVÁ CS
Department of Atomic Physics,
Polytechnical University,
Budapest, Hungary
Abstract
FOUNDATION OF THE THEORY OF DIATOMIC MOLECULES.

General remarks on observed spectra; 1. The theory of diatomic molecules; 1.1. Wave equation and
its approximate solution; 1 . 2 . Interactions of the electron spin; 1 . 3 . Matrix elements arising from the terms
neglected on the separation of the wave equation; 1 . 4 . Perturbation matrix of the centrifugal term;
1. 5. Perturbation calculation; 2. Multiplet term formulas; 2 . 1 . Doublet terms; 3. Perturbation in the
spectra; 3.1. General theory of perturbations; 4. Intensity distribution in rotational bands; 4 . 1 . General
theory and selection rules; 4 . 2 , Intensity distribution among spin multiplets.
G E N E R A L R E M A R K S ON O B S E R V E D S P E C T R A
O n t h e b a s i s of e x p e r i m e n t a l d a t a a t a b l e c a n b e c o m p i l e d of q u a n t i t i e s
d e s c r i b i n g c e r t a i n p r o p e r t i e s of t h e m o l e c u l e , w h e r e t h e w a v e n u m b e r of
any s p e c t r a l l i n e w i l l be t h e d i f f e r e n c e b e t w e e n two t a b u l a t e d v a l u e s , i . e .
v = F' - F" (1)
The tabulated quantities F a r e called s p e c t r a l t e r m s . F o r the s p e c t r a l

t e r m s of t h e s i m p l e s t s p e c t r a we h a v e a w e l l - k n o w n e m p i r i c a l f o r m u l a t h a t
c a n be w r i t t e n in t h e f o l l o w i n g f o r m
F = F e l + u e ( v + è ) - u e x e ( v + è ) 2 + . . . + B V J ( J + 1) - D v J 2 ( J + l ) 2 (2)
where
Bv = B e - a e ( v + l ) - ...; Dv= De+Te(v+1) (3)
The s y m b o l s v and J a r e i n t e g e r - v a l u e d v a r i a b l e s ; the o t h e r s y m b o l s

denote constants.
In t h e s i m p l e s t c a s e , t h e w a v e n u m b e r of a s p e c t r a l l i n e i s t h e d i f f e r e n c e
b e t w e e n two t e r m s , a s m e n t i o n e d a b o v e .
T h e " t h r e e - f o l d s t r u c t u r e " i s t h e l i n e - b a n d - b a n d s y s t e m of t h e m o l e c u l a r
spectra.
M o r e c o m p l i c a t e d s p e c t r a a r e the m u l t i p l e t s p e c t r a and so t h e m u l t i p l e t
m o l e c u l a r t e r m s . H e r e we h a v e to c o n s i d e r t h e s e l e c t i o n r u l e s , t h e
i n t e n s i t y of t h e s p e c t r a l l i n e s , p e r t u r b a t i o n , a n d p r e d i s s o c i a t i o n in t h e
molecular spectra.
377
378 KOVÁ CS
1. THE THEORY O F DIATOMIC M O L E C U L E S
A c c o r d i n g t o B o h r ' s p o s t u l a t e s , t h e f r e q u e n c y ~v of t h e e m i t t e d o r
a b s o r b e d light d e p e n d s on t h e r e s p e c t i v e e n e r g i e s , W and W " , of the h i g h e r
and l o w e r s t a t e
hv = W' - W" (4)
where h is Planck's constant.

T h e w a v e n u m b e r of a line i s
W' W"
he " he (5)
C o m p a r i n g E q . (5) with E q . (1) we obtain
The f i r s t t a s k in t h e i n t e r p r e t a t i o n of a s p e c t r u m , i s , t h e r e f o r e , to
e s t a b l i s h the t e r m s o r , in o t h e r w o r d s , t h e e n e r g y l e v e l s of t h e s t a t i o n a r y
states.
M o l e c u l a r m o d e l s : s t a t i o n a r y m o l e c u l e , a n h a r m o n i c o s c i l l a t o r and
s y m m e t r i c top.
T y p e s of e n e r g y : e l e c t r o n i c e n e r g y , v i b r a t i o n a l e n e r g y , and r o t a t i o n a l
e n e r g y . T h e f i r s t p a r t of E q . ( 2 ) i s , e x c e p t f o r the c o n s t a n t he, t h e e l e c t r o n i c
e n e r g y ; the s e c o n d p a r t is the v i b r a t i o n a l e n e r g y and the t h i r d p a r t i s the
rotational energy.
1.1. W a v e e q u a t i o n and i t s a p p r o x i m a t e solution
T h e wave equation of a m o l e c u l e with m o v i n g nuclei t a k e s t h e following

form:
[ H(xj, . . . , y x Zl, . . ., r, e,u, šlx, . . ., šly, . . ., §lz, . . . ) - w]

x ФЧ (XJ, . . . , У Г ZJ, . .. , r , e,U) =0 (?)
w h e r e Xj, . . . ,y1, . . . , z1, . . . a r e the p o s i t i o n a l c o - o r d i n a t e s of t h e e l e c t r o n s

in the s p a c e - f i x e d s y s t e m , r i s t h e i n t e r n u c l e a r d i s t a n c e , 0 and и c h a r a c t e r i z e
the p o s i t i o n of t h e i n t e r n u c l e a r d i s t a n c e in t h e s p a c e - f i x e d s y s t e m , š],x, š^y,
s k z a r e t h e P a u l i s p i n - o p e r a t o r c o m p o n e n t s f o r the k - t h e l e c t r o n in the s p a c e -
fixed s y s t e m .
Since in t h e c a s e of s l o w e r r o t a t i o n t h e i n f l u e n c e of the e l e c t r o n spin on
the m o t i o n of t h e m o l e c u l e i s g r e a t e r than t h e i n f l u e n c e of n u c l e a r r o t a t i o n ,
it i s a d v i s a b l e to e x a m i n e t h e e n t i r e wave equation in a c o - o r d i n a t e s y s t e m
Ç, r\, Ç m o v i n g t o g e t h e r with t h e m o l e c u l e . I n t r o d u c i n g t h i s s y t e m f o r t h e
p o s i t i o n a l c o - o r d i n a t e s and f o r t h e s p i n - o p e r a t o r c o m p o n e n t s , the d e t a i l e d
f o r m of t h e wave, e q u a t i o n r e a d s i
IAEA-SMR-12/32,35 379
Ha -
STTV2
90 эе
+ c o s e c 2д I JL i P j cos 0 - iP„ s i n í - W Г (8)

Эи
ч
where
-ft2 2
| Э2 | Э2
Ha = - + V + V
el,nucl(5iî'?i-r) + H
2m if эг,2 aç? „uclW aK)
(9)
and ц - MjMg/fMj-t- M 2 ) i s the r e d u c e d m a s s of the m o l e c u l e .
T h e f i r s t t e r m of (9) i s t h e k i n e t i c - e n e r g y o p e r a t o r of the e l e c t r o n s of a
m o l e c u l e with f i x e d n u c l e i e x p r e s s e d in t h e m o l e c u l e - f i x e d s y s t e m ;
Vnuclí1-) = Z j Z 2 e 2 / r i s the m u t u a l p o t e n t i a l e n e r g y of the n u c l e i ;
êl.nucl (?i » Vj, Çj. r ) i s t h e Coulomb p o t e n t i a l of t h e e l e c t r o n s with r e s p e c t to
t h e n u c l e i and to e a c h o t h e r ; Н|(ст.) r e p r e s e n t s the s p i n - i n t e r a c t i o n t e r m s
e x p r e s s e d in t h e m o l e c u l e - f i x e d s y s t e m (a d e t a i l e d f o r m will b e given l a t e r ) .
The o p e r a t o r s P E , P , P £ c o r r e s p o n d to the c o m p o n e n t s f , ц, Ç of t h e r e s u l t a n t
a n g u l a r m o m e n t u m of t h e e l e c t r o n s , i . e . the c o m p o n e n t s f , rj, Ç of t h e
r e s u l t a n t of the o r b i t a l a n g u l a r m o m e n t a and the spin m o m e n t a , e x p r e s s e d
in the m o l e c u l e - f i x e d s y s t e m . The d e t a i l e d f o r m of one of t h e m i s
/ ' i
(4 k£ + S ) = L (10)
k|
k
k=l k=l
CTj, . . . ,crf r e p r e s e n t the spin o r i e n t a t i o n s r e l a t i v e to t h e Ç a x i s .

B y o m i t t i n g c e r t a i n m e m b e r s , to be dealt with in d e t a i l l a t e r , E q . (9)
can b e solved by an e i g e n f u n c t i o n of the following f o r m :
Ф„ r.e.u) П.Л, £ (Ci.li.Çi.CTi.r)

° i — °f
X Rn v ( r ) u j п м(0,ш) (И)
Substituting t h i s into (9) we obtain
[H a - W 0 ( r ) ] E ,a;,r) = 0 (12)
— J - W 0 (r) - W rot (r) - U(r) + W j R n v ( r ) = 0 (13)

о 2 ЦГ
OTT 2 Эг
О
Э2
cotg0— + —- + cosec - i ficosI
, 2 2 дв дв* Эи
jlT |Ur
+ w
™t (r)} = 0 (14)
3 8 0 KOVÁ CS
In E q . (11) Л and Г a r e t h e q u a n t u m n u m b e r s of the c o m p o n e n t s p a r a l l e l to

t h e i n t e r n u c l e a r a x i s of the r e s u l t a n t o r b i t a l a n g u l a r m o m e n t u m and spin
m o m e n t u m of t h e e l e c t r o n s (Ci = Л + ty, and n d e n o t e s t h e r e m a i n i n g
q u a n t u m n u m b e r s of the e l e c t r o n s .
In E q . ( 1 2 ) W 0 (r) i s the eigenvalue of the m o l e c u l e with fixed n u c l e i (the
s t a t i o n a r y m o l e c u l e ) ; it c o n t a i n s the i n t e r n u c l e a r d i s t a n c e a s a p a r a m e t e r .
When m a n y e l e c t r o n s a r e involved, the e x a c t solution of t h i s e q u a t i o n i s
d i f f i c u l t , f r o m t h e m a t h e m a t i c a l point of v i e w , but the u s e of s i m p l i f y i n g
a s s u m p t i o n s h e l p s in obtaining a p p r o x i m a t e e i g e n f u n c t i o n s .
In o r d e r to c a l c u l a t e W, t h e t o t a l e n e r g y of the m o l e c u l e ^ q . (13) m u s t
b e s o l v e d . F o r t h i s p u r p o s e , t h e f o r m s of W r o t (r) and W 0 ( r ) m u s t be known.
T h e y a r e , h o w e v e r , t h e s o l u t i o n s of (14) and (12), r e s p e c t i v e l y .
A s known f r o m q u a n t u m m e c h a n i c s , E q . (14) i s t h e w a v e equation of t h e
s y m m e t r i c t o p . I t s e i g e n v a l u e h a s t h e following f o r m :
w r + 1
r o t ( ) [ J ( J ) В (15)
8it цг
w h e r e J i s t h e r o t a t i o n a l q u a n t u m n u m b e r which can a s s u m e t h e v a l u e s
I Ci I, I Ci + 1 I , . . . . T h e f o r m of t h e e i g e n f u n c t i o n i s
u J>fi>M ( e . u ) = N x s / 2 ( l - x ) d / 2 F ( l + d + s + p, - p, 1 + s, х ) е Ш ш (16)
where
x = l ( l + cos0); s = IM + Ci j ; d = | M - Ci |
p = J - ! (d+ s); M = - J , - J + l , +J
N
[~ ) (s+p) '. (d+s-fp)'. (l+d+s+2p)
4тгр'. (d+p) ! ( s )
(17)
T h e h y p e r g e o m e t r i c f u n c t i o n F i s of the f o r m
F (1 + d+ s + p , - p , 1 + s , x) = — [xp+s(l-x)P+d ] (18)
(S+Pb dxP
To s o l v e E q . (13) it i s a l s o n e c e s s a r y to know W 0 (r) o r , at l e a s t , i t s

d e p e n d e n c e on r . Since (12) cannot be solved in g e n e r a l , it is u s u a l to m a k e
s o m e a p p r o x i m a t e a s s u m p t i o n a s to the d e p e n d e n c e of W 0 (r) on r . A p o s s i b l e
one i s t h e M o r s e a p p r o x i m a t i o n which h a s t h e following f o r m :
-a(r-rl
W 0 (r) = W e l + D 1 - e (19)
w h e r e We2 i s t h e v a l u e of t h e p o t e n t i a l c u r v e at e q u i l i b r i u m i n t e r n u c l e a r
d i s t a n c e ( r e ) , D i s the d i s s o c i a t i o n e n e r g y a s r e f e r r e d to t h i s e q u i l i b r i u m ,
and a i s a c o n s t a n t c h a r a c t e r i s t i c of the e l e c t r o n i c s t a t e in q u e s t i o n ( F i g . l ) .
S u b s t i t u t i n g (19) a n d (15) i n t o (13) (neglecting U(r), which i s t h e diagonal
p a r t of t h e n e g l e c t e d t e r m s , s e e l a t e r ) and d e t e r m i n i n g the e i g e n v a l u e W
IAEA - S M R - 1 2 / 4 2 381
FIG. 1. Schematic Morse potential function.
will now y i e l d t h e t o t a l e n e r g y of t h e m o l e c u l e . E q u a t i o n (13) i s the wave

e q u a t i o n of an a n h a r m o n i c o s c i l l a t o r . F o r t h e e i g e n v a l u e of t h e equation
we obtain (divided by he)
F - F e l + u e ( v + è) - u e x e ( v + i ) 2 + B v [ J ( J + 1) -Г2 2 ] - D v [ J ( J + 1 ) - qY
(20)
w h e r e v i s t h e v i b r a t i o n q u a n t u m n u m b e r and
W'el _a ПГ ê
• el : üe Xe
he " С7Г V 2ц " 4D
Bv = В e - * e ( v + | ) ; D v = De; Be (21)
8ТГ 2 МСГ 2 '
B„ 4B
«e = 2B
e*e ; De
"exe J
and t h e e i g e n f u n c t i o n i s a c t u a l l y a g e n e r a l i z e d L a g u e r r e p o l y n o m i a l .
T h e e x p r e s s i o n (20) c o m p a r e s m o s t f a v o u r a b l y with t h e e m p i r i c a l
f o r m u l a (2). T h e s t r u c t u r e of t h e e m p i r i c a l f o r m u l a i s now c l e a r , a s w e l l
a s the o r i g i n of i t s d e n o t a t i o n . In t h e f i r s t t e r m of (20), W e i c o r r e s p o n d s
(by (19)) to t h e m i n i m u m of the p o t e n t i a l c u r v e in F i g . 1 a n d , s i n c e t h i s v a l u e
d e p e n d s on t h e e l e c t r o n c o n f i g u r a t i o n only, it i s called e l e c t r o n i c e n e r g y .
T h e s e c o n d and t h i r d t e r m s a r e t h e e n e r g y of t h e a n h a r m o n i c o s c i l l a t o r ,
the t e r m b e f o r e t h e l a s t is the e n e r g y of t h e s y m m e t r i c top, which a l s o
a c c o u n t s f o r the c h a n g e of the i n t e r n u c l e a r d i s t a n c e in t h e h i g h e r v i b r a t i o n a l
s t a t e , and t h e l a s t t e r m is the c e n t r i f u g a l c o r r e c t i o n , a r i s i n g f r o m the
i n c r e a s e in i n t e r n u c l e a r d i s t a n c e d u r i n g h i g h e r - e n e r g y r o t a t i o n .
T h e m o l e c u l a r m o d e l and the e x a c t w a v e - m e c h a n i c a l t r e a t m e n t l e a d to
s i m i l a r r e s u l t s a s long a s t h e s e p a r a t i o n of t h e wave equation c a n b e e f f e c t e d o r ,
m o r e p r e c i s e l y , a s long a s t h e t e r m s o m i t t e d on s e p a r a t i o n a r e r e a l l y n e g l i g i b l e .
A c c o r d i n g to the c h a r a c t e r i z a t i o n of the e l e c t r o n i c s t a t e s by t h e q u a n t u m
n u m b e r A, t h e p a r a l l e l c o m p o n e n t of t h e r e s u l t a n t o r b i t a l a n g u l a r m o m e n t u m
of the e l e c t r o n s to the i n t e r n u c l e a r a x i s : f o r Л= 0, 1, 2, . . . , t h e s y m b o l s
of the m o l e c u l a r t e r m s a r e L, П, Д, . . . .
In t h e q u a n t u m - m e c h a n i c a l t r e a t m e n t , t h e s t a t e s b e l o n g i n g to t h e p o s i t i v e
and n e g a t i v e v a l u e s of Л a r e d e g e n e r a t e and t h e c o r r e s p o n d i n g e i g e n f u n c t i o n s
a r e l i n e a r c o m b i n a t i o n s of o p p o s i t e s y m m e t r y of t h e e i g e n f u n c t i o n s belonging
to t h e p o s i t i v e and n e g a t i v e v a l u e s of Л,
382 KOVÁCS
1
+
кл L
Ф+л Ф-л
JT
1
(22)
-Ф-А
J2
Under i n c r e a s i n g r o t a t i o n , h o w e v e r , t h e t e r m s e x p r e s s i n g t h e coupling of
e l e c t r o n i c m o t i o n to t h e r o t a t i o n of the n u c l e i — which have b e e n n e g l e c t e d
in o u r f i r s t a p p r o x i m a t e solution of the wave equation — r e s u l t ( p e r t u r b a t i o n
t h e o r y ) in a s p l i t t i n g of t h i s t w o - f o l d d e g e n e r a t e s t a t e . T h i s p h e n o m e n o n i s
c a l l e d A - t y p e doubling o r s p l i t t i n g .
1.2. I n t e r a c t i o n s of t h e e l e c t r o n spin
Most of t h e o b s e r v e d m o l e c u l a r s p e c t r a exhibit a m u l t i p l e t s t r u c t u r e .
T h e m u l t i p l y i n g of a s p e c t r a l line i s due to t h e m u l t i p l y i n g of t h e t e r m s
i n v o l v e d in t h e t r a n s i t i o n , giving r i s e to t h e line in q u e s t i o n . It i s l o g i c a l to
r e f e r t h i s m u l t i p l e t s t r u c t u r e of the t e r m s to the e l e c t r o n s p i n , a s i s done
in t h e c a s e of m u l t i p l e t s p l i t t i n g in a t o m i c s p e c t r a .
O
Ü
FIG. 2. Connection between spin vector and molecular axis in a molecule at rest.
T h e s p i n s of the i n d i v i d u a l e l e c t r o n s f o r m a r e s u l t a n t spin v e c t o r Š,
w h o s e m a g n i t u d e i s d e f i n e d by t h e spin q u a n t u m n u m b e r S. T h e r e i s an
i n t e r a c t i o n b e t w e e n t h e m a g n e t i c f i e l d s of the m o v i n g e l e c t r o n s and nuclei
on the one hand and t h e r e s u l t a n t spin on the o t h e r . T h e i n t e r a c t i o n b e t w e e n
the spin and the p a r a l l e l component of t h e r e s u l t a n t o r b i t a l a n g u l a r m o m e n t u m
of t h e e l e c t r o n s in the s t a t i o n a r y m o l e c u l e m a k e s the r e s u l t a n t spin v e c t o r 3
p r e c e s s r o u n d t h e i n t e r n u c l e a r a x i s in s u c h a m a n n e r that i t s p a r a l l e l
c o m p o n e n t i s Г/ři ( F i g . 2), w h e r e E i s t h e q u a n t u m n u m b e r . L can a s s u m e
any one of t h e 2 S + 1 v a l u e s , S, S - l , . . . , - S + l , - S . T o an e l e c t r o n i c s t a t e of
a g i v e n Л t h e r e belong 2S+1 s u b s t a t e s — a c c o r d i n g to t h e p o s s i b l e o r i e n t a t i o n s
of the 3 spin — whose e n e r g y l e v e l s a r e evenly s p a c e d to a good a p p r o x i m a t i o n .
T h i s i s why the n u m b e r 2S+1 i s c a l l e d the m u l t i p l i c i t y of t h e e l e c t r o n i c s t a t e
in q u e s t i o n ; it i s u s e d a s a l e f t - h a n d s u p e r s c r i p t to t h e t e r m s y m b o l s
2
П, 3 Д , e t c . ) . E a c h s u b s t a t e could be c h a r a c t e r i z e d by t h e a p p r o p r i a t e
v a l u e of t h e q u a n t u m n u m b e r E; i n s t e a d , the s u m fž = A + E i s n o r m a l l y
u s e d , h o w e v e r ; it is given a s a r i g h t - h a n d s u b s c r i p t ( nQ, П , П2).
T h e r o t a t i o n of t h e m o l e c u l e a f f e c t s t h e i n t e r a c t i o n s . Hund w a s f i r s t to
e x a m i n e t h i s p h e n o m e n o n , and t h e v a r i o u s l i m i t i n g - c a s e m o d e l s i n t r o d u c e d
by h i m , he c a l l e d c a s e s a, b, c, d and e .
IAEA - S M R - 1 2 / 4 2 383
In Hund 1 s c a s e (a) ( F i g . 3 ) , r o t a t i o n i s a s s u m e d to h a v e little i n f l u e n c e

on t h e conditions e x i s t i n g in t h e f i x e d m o l e c u l e . In o t h e r w o r d s , t h e spin i s
s o s t r o n g l y coupled to t h e i n t e r n u c l e a r axis that i t s p a r a l l e l component
r e m a i n s q u a n t i z e d even in the r o t a t i n g m o l e c u l e , so that F r e m a i n s a good
q u a n t u m n u m b e r . T h e m o l e c u l e t h e r e f o r e b e h a v e s a s a s y m m e t r i c top
w h o s e a n g u l a r m o m e n t u m with r e s p e c t to t h e i n t e r n u c l e a r a x i s is defined
by Í2, while i t s t o t a l a n g u l a r m o m e n t u m i s given by t h e q u a n t u m n u m b e r J;
J can a s s u m e the values |fi + l | , . . . ( F i g . 3 ) . In t h i s c a s e , which is
i d e n t i c a l to the c a s e d e s c r i b e d q u a n t u m m e c h a n i c a l l y in t h e p r e v i o u s l e c t u r e s ,
a s e p a r a b l e w a v e e q u a t i o n can be d e r i v e d . When t h e i n t e r a c t i o n b e t w e e n
s p i n a n d r o t a t i o n i s e x a m i n e d , t h e t e r m s n e g l e c t e d on t h e s e p a r a t i o n of the
wave e q u a t i o n can be t a k e n into a c c o u n t by m e a n s of a p e r t u r b a t i o n
calculation.
FIG. 3. Vector model of Hund's case (a).
FIG.4. Vector model of Hund's case (b).
In H u n d ' s c a s e (b) t h e spin i s not coupled to t h e i n t e r n u c l e a r a x i s . The

m o l e c u l e r o t a t e s a s if t h e r e w e r e no spin: t h e r e s u l t a n t N i s c o m p o s e d of Л
and t h e (unquantized) a n g u l a r m o m e n t u m R of t h e r o t a t i o n of t h e n u c l e i
( F i g . 4 ) . T h e m a g n i t u d e of N i s d e f i n e d by t h e q u a n t u m n u m b e r N;
N = | a | , IA + 1 I, . . . . T h e r e f o r e N plays t h e s a m e r o l e h e r e a s J d o e s in
t h e s i n g l e t s t a t e s . In t h e c a s e of a s t r o n g r o t a t i o n , t h e spin S will b e only
w e a k l y coupled to the i n t e r n u c l e a r a x i s and m a y be r e g a r d e d a s p r a c t i c a l l y
f r e e . It will b e c o n s e q u e n t l y c o m b i n e d with N to give the t o t a l a n g u l a r
m o m e n t u m of t h e r o t a t i n g m o l e c u l e . The s y m b o l f o r t o t a l a n g u l a r m o m e n t u m
i s t h e u s u a l o n e , J . T h e q u a n t u m n u m b e r J , d e t e r m i n i n g t h e m a g n i t u d e of
J , can a s s u m e t h e v a l u e s N+S, N + S - . . . , | N-S | . In t h i s c a s e too, S c a n
b e o r i e n t e d in 2S+1 w a y s f o r a given N (provided, a s u s u a l , that N ^ S ) .
384 KOVÁ CS
H e n c e , e a c h N l e v e l i s s p l i t into 2S+1 s u b l e v e l s , but t h e e n e r g y d i f f e r e n c e s

b e t w e e n t h e s e a r e z e r o in the ideal c a s e (b).
F o r a r i g o r o u s w a v e - m e c h a n i c a l study of spin i n t e r a c t i o n s , the e l e c -
t r o n i c p a r t of the wave e q u a t i o n d i s c u s s e d p r e v i o u s l y i s to be a n a l y z e d in
d e t a i l . F i r s t let u s find the t e r m s m a k i n g up t h e o p e r a t o r H a in (9). T h e
B r e i t wave e q u a t i o n f o r a t o m s containing two e l e c t r o n s h a s the P a u l i
a p p r o x i m a t i o n and, in t h e a b s e n c e of e x t e r n a l f i e l d s , s i x we 11-se p a r a b l e
g r o u p s of t e r m s . T h e e l e c t r o n spin o c c u r s only in two g r o u p s . One of
t h e m d e s c r i b e s t h e s p i n - o r b i t i n t e r a c t i o n , i . e . t h e i n t e r a c t i o n b e t w e e n the
m a g n e t i c m o m e n t u m a s s i g n e d to the o r b i t a l a n g u l a r m o m e n t u m of the e l e c -
t r o n s and the spin m a g n e t i c m o m e n t s ; t h e o t h e r c o r r e s p o n d s to t h e i n t e r -
a c t i o n b e t w e e n the m a g n e t i c dipole m o m e n t s of the two e l e c t r o n s p i n s , i . e .
t o t h e s p i n - s p i n i n t e r a c t i o n . In the d i s c u s s i o n of t h e i n t e r a c t i o n of e l e c t r o n
s p i n s in m o l e c u l e s with m o r e t h a n two e l e c t r o n s , it s e e m s convenient to
adopt s i m i l a r t e r m s and to c o m p l e m e n t t h e f o r m u l a with a t e r m which
r e s u l t s f r o m t h e r o t a t i o n of t h e m o l e c u l e ( s p i n - r o t a t i o n i n t e r a c t i o n ) and
which, t h e r e f o r e , h a s no equivalent in a t o m s . A c c o r d i n g l y , t h e l a s t t e r m
of (9) in t h e m o l e c u l e - f i x e d s y s t e m will b e
H?a 4(a.i ') = H as o + Has s + HaSR s(23)

'
w h e r e t h e f i r s t t e r m on t h e r i g h t - h a n d s i d e i s t h e s p i n - o r b i t i n t e r a c t i o n ,
and t h e s e c o n d and t h i r d t e r m s d e s c r i b e t h e s p i n - s p i n and s p i n - r o t a t i o n
i n t e r a c t i o n s , r e s p e c t i v e l y . Let us e x a m i n e t h e s e t e r m s s e p a r a t e l y .
(a) S p i n - o r b i t i n t e r a c t i o n . As is w e l l - k n o w n , t h e s p i n - o r b i t i n t e r -
a c t i o n h a s t h e following f o r m :
H?°
w h e r e f k and s k a r e t h e o r b i t a l a n g u l a r m o m e n t u m and s p i n m o m e n t u m of
the k - t h e l e c t r o n , r e s p e c t i v e l y ,
he f 1 3V\
47Г т г с А N /k
and - ( 9 V / 3 r ) k i s t h e v a l u e of t h e e l e c t r i c f i e l d s t r e n g t h in t h e p l a c e of t h e
k-th electron.
U s i n g t h e a p p r o p r i a t e e i g e n f u n c t i o n s , it can b e shown that the m a t r i x
e l e m e n t s of (24) a r e d i f f e r e n t f r o m z e r o only if, s i m u l t a n e o u s l y , AS = 0, ± 1
and ДО = 0 in s u c h a way that e i t h e r ДА = ДЕ = 0 o r Д Л = - Д Е = ± 1. It i s
g e n e r a l p r a c t i c e to a s s u m e t h a t (24) f o r ДБ = 0 h o l d s in t h e following f o r m :
H®° = A ( L S ) (26)
w h e r e L and Š a r e the o p e r a t o r s of t h e r e s u l t a n t o r b i t a l a n g u l a r m o m e n t u m
and r e s u l t a n t s p i n m o m e n t u m of the e l e c t r o n s , r e s p e c t i v e l y .
T h e m a t r i x e l e m e n t s of (26) have t h e f o r m
<n,v,A,E |Hso| n,v,A,E> = AAE (27a)

IAEA - S M R - 1 2 / 4 2 385
< n , v , Л, E |Н®°| n ' , v ' , Л ± 1 , E+l>
-<n,v,A|AL I n 1 , v ' , Л ± 1 У N/S(S+1) - E(E+1) (27b)
where
< n,v, Л | Â L J n ' , v', Л± 1 >
=/ ) J r ф*
n,A
. R*
n,v
A v( r ') L с£ ф
v .
n , Si1
Л± 1 R n .,v , r 2 d r d r 1 (28)'
|
A
a n d Lg i s t h e Ç c o m p o n e n t of t h e o p e r a t o r L .
In o r d e r t o c a l c u l a t e t h e v a l u e s of the m a t r i x e l e m e n t s f o r t h e c a s e
AS = ± 1 ( s o - c a l l e d i n t e r c o m b i n a t i o n p e r t u r b a t i o n s ) o n e m u s t know t h e e x a c t
e l e c t r o n c o n f i g u r a t i o n a n d t h e f o r m s of t h e c o r r e s p o n d i n g e i g e n f u n c t i o n s .
(b) S p i n - s p i n i n t e r a c t i o n . U s i n g H e i s e n b e r g ' s m e t h o d , t h e s e c o n d t e r m
of (23) c a n b e w r i t t e n in t h e f o l l o w i n g f o r m :
2 2
H
~ss
s s = _ n _h ee Г\ -3<škřkk')(šk'řkk-)+ (sA')r2kk.
л 2 2
тп г с г2 Z_i Г '
a
Г
4тг k,>k кк
F o r the m a t r i x element we obtain
< n , v . A , E |H® S | n , v , A , E> = < n , v, Л | ë | n , v , A > [ 3 E 2 - S ( S + 1)] (29b)
<n,v,A,E | Ř f | n',v',A±l,E + l >
= £ < n , v, A I n ' , v ' , A ± l > ( 2 E + 1 ) ч/ S ( S + 1 ) - E ( E + 1) (29c)
< n , v , A, E | H S S I n ' , v 1 , A ± 2, E * 2 >
= i < n , v, A |ö"| n ' , v ' , A ± 2 > «J [ S (S + 1 ) - E ( E i 1 )] [ S (S + 1 ) - ( E + 1 )(EŤ 2)]

(29d)
(с) S p i n - r o t a t i o n i n t e r a c t i o n . T h e t h i r d t e r m of (23) h a s no c o u n t e r p a r t
i n t h e e x p r e s s i o n f o r a t o m s . It w a s K r a m e r s who f i r s t p o i n t e d out t h a t ,
s i n c e t h e o p e r a t o r H®0 c o n t a i n s t h e v e l o c i t i e s of t h e e l e c t r o n s a s w e l l , t h e
m a g n e t i c f i e l d s e t up by t h e r o t a t i o n of t h e n u c l e i a f f e c t s t h e e l e c t r o n s p i n s
a l s o in a n o t h e r w a y , not d e a l t w i t h s o f a r , w h i c h g i v e s r i s e to a new t e r m
i n t h e p e r t u r b a t i o n p o t e n t i a l (23).
T h e s e a d d i t i o n a l t e r m s , a s shown by t h e d e t a i l e d c a l c u l a t i o n , h a v e t h e
following f o r m :
H F = 7(RŠ)=Ť[(Ň-NS)ŠJ = 7 [ (NS) - AS] = 7 [(J-Š)Š-AŠ]
= Ť { Š 2 - S 2 + é [ ( J e + i J „ ) ( S s - i S 4 ) + (J £ - i ^ H S j + iS,,)]} (30)
F o r t h e f i r s t t w o t e r m s in t h e l a s t e x p r e s s i o n of (30), Д Е = 0; f o r t h e o t h e r
two t e r m s , Д Е = ± 1 . T h e e x p l i c i t f o r m s of t h e m a t r i x e l e m e n t s a r e
386 KOVXCS
< n , v , Л, I n , v , A, E > = < n , v , A | т | n , v , A > [ £ 2 - S ( S + l ) ] (31a)
<n,v,A, |n,v,A, £±1> = <n,v,A |Ť|n,v,A>
X [J(J+1) - n(i}±l)]1/2[S(S+l) - Z (E±l)]1/2 (31b)
T h e e n e r g y t e r m s and p e r t u r b a t i o n m a t r i x e l e m e n t s c o n s i d e r e d so f a r in
t h e e l e c t r o n spin i n t e r a c t i o n a r e p r o v i d e d by t h e H a m i l t o n i a n of t h e
e l e c t r o n i c p a r t of the wave equation.
In f o r m u l a s (12) and (13) t h e t e r m s a r i s i n g f r o m H^(cr ; ) should be
r e c o r d e d s e p a r a t e l y , t o g e t h e r with the e l e c t r o n e n e r g i e s W 0 ( r ) . T h i s i s
l a r g e l y due t o the f a c t that W 0 (r) r e f e r s only to that p a r t of H a which d o e s
not c o n t a i n t h e spin, a s w e l l a s to t h e f a c t t h a t t h e t e r m s m e n t i o n e d above
and t h e d i a g o n a l m a t r i x e l e m e n t s c o n n e c t e d with t h e m play an i m p o r t a n t
r o l e in f o r m i n g t h e m u l t i p l e t s t r u c t u r e of t h e t e r m s in H u n d ' s l i m i t i n g
c a s e s (a) and (b), and in the i n t e r m e d i a t e c a s e b e t w e e n t h e m .
1.3. M a t r i x e l e m e n t s a r i s i n g f r o m the t e r m s n e g l e c t e d on s e p a r a t i o n of
t h e wave equation
A m o l e c u l e in slow r o t a t i o n g e n e r a l l y a p p r o x i m a t e s H u n d ' s c a s e (a),

w h e r e the r e s u l t a n t s p i n m o m e n t u m S i s coupled to the i n t e r n u c l e a r a x i s ,
w h e r e a s f o r i n c r e a s e d r o t a t i o n Hund's c a s e (b) p r o v i d e s a b e t t e r a p p r o x i -
m a t i o n , w h e r e S i s coupled to t h e v e c t o r N. It i s a l s o evident that a s t h e
m o l e c u l e g r a d u a l l y p a s s e s f r o m a s t a t e of slow r o t a t i o n t o one of i n c r e a s e d
r o t a t i o n , t h e decoupling of^the spin m o m e n t u m f r o m t h e m o l e c u l a r a x i s and
i t s coupling to the v e c t o r N a l s o o c c u r s g r a d u a l l y . In a q u a n t u m - m e c h a n i c a l
t r e a t m e n t of this g r a d u a l change the s p i n - d e p e n d e n t p a r t s of t h e t e r m s
n e g l e c t e d on s e p a r a t i o n should also be taken into a c c o u n t .
Although t h e r e s u l t a n t o r b i t a l a n g u l a r m o m e n t u m h i s f a r m o r e s t r o n g l y
c o u p l e d to t h e i n t e r n u c l e a r a x i s than t h e spin m o m e n t u m the i n c r e a s i n g
r o t a t i o n m u s t a l s o have s o m e effect upon Ü. It h a p p e n s i n d e e d , p a r t i c u l a r l y
in light m o l e c u l e s , t h a t if t h e a x i a l f i e l d a l o n g t h e i n t e r n u c l e a r a x i s i s not
v e r y s t r o n g , s t r o n g r o t a t i o n r e s u l t s in t h e decoupling of t h e v e c t o r L f r o m
the i n t e r n u c l e a r a x i s ; L i s then coupled to t h e a x i s of r o t a t i o n . T h i s i s
H u n d ' s c a s e (d) ( F i g . 5). T h i s i n c i p i e n t decoupling of v e c t o r however,
i s not r e s t r i c t e d to light m o l e c u l e s ; it i s e v e n q u i t e a f r e q u e n t p h e n o m e n o n .
It r e s u l t s in the s p l i t t i n g of the two d e g e n e r a t e s t a t e s of d i f f e r e n t s y m m e t r y
a r i s i n g f r o m t h e o r i e n t a t i o n s + Л and - A; t h i s i s t h e p r e v i o u s l y m e n t i o n e d
L / T N S
FIG. 5. Vector model of Hund's case (d).

IAEA - S M R - 1 2 / 4 2 387
Л - t y p e s p l i t t i n g . It c a n t h e r e f o r e b e s t a t e d t h a t Л - t y p e d o u b l i n g r e f l e c t s on
t h e e a r l y s t a g e of t h e g r a d u a l t r a n s i t i o n f r o m c a s e (a) o r c a s e (b) to c a s e (d).
F o r t h e q u a n t u m - m e c h a n i c a l t r e a t m e n t of t h i s g r a d u a l t r a n s i t i o n , on t h e
b a s i s of p e r t u r b a t i o n t h e o r y , t h e p a r t s d e p e n d i n g o n t h e o r b i t a l m o m e n t u m L
of t h e t e r m s n e g l e c t e d w h e n s e p a r a t i n g the w a v e e q u a t i o n s a r e a l s o u s e d .
L e t u s now s t u d y t h e s e t e r m s . T h e p a r t of t h e n e g l e c t e d t e r m s
d e p e n d i n g o n t h e r o t a t i o n a l c o - o r d i n a t e s h a s the f o l l o w i n g f o r m :
HPa= < n . v , Í Í . J i H P j n - . V . n - . J - > = / < v . n i J H ^ n . i V . i 0 . i r d T (32)
where
hi { 2 + ct
H Pl a = ^ дв §e) + 2
собесе - i c t g f l ( P 4 P t + Р£Р„) (33)
2 2
87Г МГ
It c a n be s h o w n t h a t (32) i s d i f f e r e n t f r o m , z e r o only if Г2* = Í2± 1 a n d J ' = J .

Then, since
P = ± iPt
v С
we h a v e
(34)
where
P4Pt+PtP 4 = ±i(2íí±l)Pe (35)
s i n c e P 5 = Q . In (34), В = h 2 /87r 2 jur 2 . T h e f i r s t p a r t of (34) c o n t a i n s only

t h e r o t a t i o n a l p a r t Uj n M ( e , u ) of t h e e i g e n f u n c t i o n ; it i s t h e s e c o n d p a r t
that contains t h e e l e c t r o n i c and v i b r a t i o n a l p a r t s , i . e . i n ! i R n v. T h e f i r s t
p a r t of (34) c a n e a s i l y b e e x p r e s s e d in t e r m s of t h e t o t a l a n g u l a r - m o m e n t u m
o p e r a t o r of t h e m o l e c u l e
± i
<Ql±le +
i l b i +
(fi±1)cotgelQ±1>
= - IJ ±IJ |N±L> = N/J ( J + 1 ) - Q (Q ± 1 ) (36)
U s i n g (36), E q . (34) c a n b e r e w r i t t e n i n t h e f o r m
H ^ = 2 < n , v , П | В Р £ I n ' , v ' , i î ± l > J J ( J + 1) - П ( П ± 1 ) (37)
where
<N n ,' v ,' t t 1I B P ÍJ1 n ' , v \ n ± l >' = J / rф* п R* B P Yф . „

n,£1 n,v £ n , 0 ± l
, Rn, ,v
, dr '
(38)'
S i n c e P 6 = L j + S E , (if n 1 = n , v 1 = v a n d Г21 = fi ± 1 a r e s u c h t h a t Л ' = Л

a n d E' = E ± 1 ) s u b s t i t u t i n g t h e s u i t a b l e f o r m of t h e e i g e n f u n c t i o n i n t o (38)
yields
388 KOVÁ CS
<n,v,A, c | B P e I n,v,A, E ± l >
= B 0 < E |S e I E ± l > = i B 0 «УS(S + 1) - E ( E ± l ) (39)
Hence
< n , v , Л, E | H P j n , v , Л, E ± 1 >
= B 0 s/S(S+l) - E ( E ± 1 ) v/J(J+1) - П ( П ± 1 ) (40)
w h e r e B 0 is t h e r o t a t i o n a l c o n s t a n t at e q u i l i b r i u m i n t e r n u c l e a r d i s t a n c e .
E x p r e s s i o n (40) d e s c r i b e s t h e i n t e r a c t i o n s b e t w e e n t h e c o m p o n e n t s of the
m u l t i p l e t t e r m s of one and the s a m e e l e c t r o n i c s t a t e , o r , in o t h e r w o r d s ,
t h o s e p e r t u r b a t i o n m a t r i x e l e m e n t s with t h e help of which t h e g r a d u a l
t r a n s i t i o n f r o m H u n d ' s c a s e (a) into c a s e (b) can b e d i s c u s s e d in a q u a n t u m -
mechanical way.
On t h e o t h e r hand, if Í2' = Q ± 1 i s s a t i s f i e d so that A' = A ± 1 and
Г,' = L , t h e n e x p r e s s i o n (37) t a k e s t h e f o r m
<n,v,A,E |HPjn',v',A±l,E>
= 2 < n, v, Л | b L £ | n ' , v \ A ± 1 > JJ(J+ 1) - Í2 (Q ± 1 ) (41)
and d e s c r i b e s the i n t e r a c t i o n a m o n g the d i f f e r e n t e l e c t r o n i c s t a t e s which,

p r o v i d e d the t e r m s a r e s u f f i c i e n t l y s e p a r a t e d , g i v e s r i s e to A - t y p e doubling.
( F o r a r i g o r o u s t r e a t m e n t E q . (41) should be c o m p l e m e n t e d with t h e m a t r i x
e l e m e n t s of s p i n - o r b i t i n t e r a c t i o n . ) It i s p a r t i c u l a r l y t h e s e t e r m s that will
p e r m i t t h e d i s c u s s i o n of p e r t u r b a t i o n a m o n g c l o s e - s p a c e d t e r m s .
L e t u s now e x a m i n e t h e o t h e r p a r t of t h e t e r m s n e g l e c t e d in t h e wave
e q u a t i o n which h a s t h e f o l l o w i n g f o r m :
uh 2
HP = ÎP2+P2Ï i f ÜÜ 2r_2 9R 2 r Эф (42)
2
2a о07Г2 /иг„2 E v> ' ф Эг Í R Эг 9 r " ф Эг
Since t h i s d o e s not contain the r o t a t i o n a l c o - o r d i n a t e s , it f o l l o w s f r o m the

o r t h o g o n a l i t y of t h e r o t a t i o n a l p a r t of t h e e i g e n f u n c t i o n t h a t only t h o s e
m a t r i x e l e m e n t s a r e n o n - z e r o f o r which A J = 0, AQ = 0, Д М = 0. Since
P 2 + P 2 = ( L , + S )2 + (L + S )2 = v(L? + L 2 ) + (Š 2 + Š 2 ) + 2(L
1 Š + L Š)
i v i ť v ч' ê т] £ v' ï ï л л .
(43)
only t h e t e r m s in t h e f i r s t two p a r e n t h e s e s of t h e l a s t e x p r e s s i o n give

diagonal e l e m e n t s with r e s p e c t to f u r t h e r q u a n t u m n u m b e r s A and E; h e n c e ,
f o r t h e s e , Д Л = ДЕ = 0. D i a g o n a l e l e m e n t s a r e a l s o o b t a i n e d f r o m t h e
s e c o n d t e r m of (42). A v e r a g i n g t h e s e t e r m s o v e r the e l e c t r o n i c c o - o r d i n a t e s ,
we obtain the d e t a i l e d f o r m of U(r) in (13) a s
u r d T
( ) = I < л . г Щ ^ п . л . Е
л
Í 9 ло лО ло \ о ™п,Л,£
'V.A.l 1 5 ( t i t L 2 ,) + (S® + s t y фп, л, Z - Г2 — - 5 - dT (44)
IAEA -SMR-12/42 389
F o r t h e c a l c u l a t i o n of t h e l a s t t e r m of (44) it i s n e c e s s a r y t o know t h e
e x p l i c i t f o r m of ф . Since t h i s t e r m i s usually s m a l l in c o m p a r i s o n with the
p r e c e d i n g o n e s and a s it depends only slightly on t h e i n t e r n u c l e a r d i s t a n c e
(so t h a t it c a n b e r e g a r d e d a s c o n s t a n t in c o m p o n e n t s of the s a m e m u l t i p l e t )
it can b e i n c o r p o r a t e d into t h e e x p r e s s i o n of Wg(r) o r W e j in E q s (13) o r (19).
T h u s , t h e d i a g o n a l m e m b e r s c o n t r i b u t i n g to t h e e n e r g y will b e
2
<s n ,j v ,•A , i Г |i н Р2 a| n1 ,' v' , A ,' E >' = J / R*n , v ÏÏ(r)R
v
' n,v r d r
= ( n , v , A | в (L 2 + n , v , A > + B 0 [ S ( S + 1) - E2] (45)
w h e r e we have m a d e u s e of the f o r m u l a s
2
J/ R*nv B R n, v r d r = B n0;
< E I S 2 + Š 2 J E> = < E I S 2 - S 2 I E > = S(S + 1) - E 2 (46)
s i n c e the v e c t o r S is c o n s t a n t . Furthermore,
< n , v , A J В ( L 2 + L^) I n, v, A >
=f (L2e+ L2) </>n,A,2Rn.vdT (47)

8ж цг
Since (47) a l s o gives i d e n t i c a l v a l u e s f o r the d i f f e r e n t c o m p o n e n t s of the

s a m e m u l t i p l e t , it is u s u a l l y a l s o i n c o r p o r a t e d in the e x p r e s s i o n of W e j .
W h e n U(r) i s t a k e n i n t o account in t h e solution of (13) t h e e x p r e s s i o n
S ( S + 1 ) - E 2 a p p e a r s within the p a r e n t h e s e s , in addition to J ( J + l ) - f 2 2 , in t h e
l a s t two t e r m s of (20).
F o r the o f f - d i a g o n a l m a t r i x e l e m e n t s , a c c o r d i n g to Van V l e c k , f o r m u l a
(42) y i e l d s t h e following e x p r e s s i o n f o r the c a s e s An f 0 and Av f 0:
< n , v , A , E I H 2 a I n ' , v 1 , A, E )>
<n|p|n'> + <n|Q|n' > T i n ' > P r R n . v - r ' d r (48)
where
2
<n|P(r)|n-> = B(r) | < A I E ( P + P 2 ) фп, AiE dr
d2
_ p <t>.
2 r A E
<n|Q(r)in- > - B ( r ) r - 2 dr
9ф
T h e f i r s t two t e r m s of (48) a r e s m a l l e r than i t s l a s t t e r m by an o r d e r of

magnitude.
390 KOVÁCS
In a d d i t i o n to t h e a b o v e t e r m s , s o m e o f f - d i a g o n a l t e r m s a r e o b t a i n e d f o r
w h i c h Д А = - Д Е = ± 1 . T h e l a s t t e r m in (43), not t a k e n i n t o a c c o u n t so f a r ,
t a k e s the following explicit f o r m :
< n , v , A, E |ЙР а I n ' . v ' , Л ± 1 , ETI)
= 2 < n , v , Л IВ L £ | n ' , v ' , A ± l > n/S(S+1) - E(E + 1) (50)
where
<n,v,A |BLjn',v',A±l> =Yf <51)

л
In t h e e x a m i n a t i o n of A - t y p e doubling and p e r t u r b a t i o n (27b) i s to b e added
t o E q . (50).
1.4. P e r t u r b a t i o n m a t r i x of t h e c e n t r i f u g a l t e r m
T h e c l a s s i c a l t r e a t m e n t of the r o t a t i n g m o l e c u l e s h o w s that t h e l a s t t e r m
of (20), t h e c e n t r i f u g a l t e r m , a r i s e s f r o m the c h a n g e i n the i n t e r n u c l e a r
d i s t a n c e due to t h e r o t a t i o n of the m o l e c u l e .
If the e l e c t r o n s p i n i s t o t a l l y u n c o u p l e d f r o m t h e i n t e r n u c l e a r a x i s b y
t h e i n c r e a s i n g s p e e d of r o t a t i o n , t h e n Í2 i s no l o n g e r d e f i n e d a n d t h e
expression
- D [ J (J + 1 ) - f2 2 ] 2 (52)
c e a s e s t o h o l d . I f , h o w e v e r , at the s a m e t i m e L i s s t i l l c o u p l e d to t h e
i n t e r n u c l e a r a x i s and s t a y s so (in o t h e r w o r d s , if H u n d ' s c a s e (b) p r e v a i l s ) ,
t h e n we can d e r i v e R 2 = Ň 2 - A 2 f r o m F i g . 4 and t h e c e n t r i f u g a l t e r m b e c o m e s
< Л, N I Н£ I Л, N > = - D [ N ( N + 1) - A 2 ] 2 (53)
T h i s f o r m u l a , h o w e v e r , i s r i g o r o u s l y v a l i d only w h e n the e l e c t r o n spin is

a l r e a d y f u l l y c o u p l e d to t h e v e c t o r N. In o r d e r t o a c c o u n t f o r t h e g r a d u a l
d e c o u p l i n g f r o m t h e i n t e r n u c l e a r a x i s and f o r t h e c o u p l i n g t o t h e v e c t o r N
we m u s t u s e t h e p e r t u r b a t i o n m e t h o d of q u a n t u m m e c h a n i c s . T h i s r e q u i r e s
the k n o w l e d g e of t h e p e r t u r b a t i o n m a t r i x . T o s e t it up, l e t u s s t a r t f r o m
(53) b y e x p r e s s i n g the v e c t o r Ň in t e r m s of t h e v e c t o r s J a n d i§. F r o m
F i g . 4 we s e e t h a t
R 2 = N 2 - A 2 = (J - S) 2 - A 2 (54)
a n d , r e p l a c i n g the v e c t o r s by t h e r e l e v a n t o p e r a t o r s , we h a v e
H c = - Ď [ Ň 2 - A 2 ] 2 = - D [ (J -Š) 2 - A 2 ] 2 = - Ď t J 2 + Š 2 - A 2 - 2 (J Š) ] 2
= - Ď [ J . 2 + Š 2 - A 2 - 2 J s S s - 2 ( J £ S 5 + J^S,,)] 2
= - Ď {[ J 2 + S 2 - A 2 - 2 J £ S £ ] 2 + 4 (J Ě Š € + J ^ ) 2
- 4 ( J 2 + Š 2 - A 2 ) (J 6 S E + J 4 S 4 ) + 4 [ J A ( J £ Š í + J 4 S 4 )
(55)
IAEA-SMR-12/11 391
P e r f o r m i n g the r e s t of the c a l c u l a t i o n in d e t a i l , t h e f o l l o w i n g m a t r i x
elements a r e obtained:
< Í 2 , E > = - D{ i f ( J , fž) + f(S, E) ] 2 + 2 f ( J , Q ) f ( S , E ) + 2 i 2 E } (56a)
< П, E | H j I fi ± 1 , E ± 1 >
- 2 D [ g ( J , Г2) + g(S, E) - 1 ] [ g ( J , Q ) g ( S , E ) r (56b)
< Q, E I j Q ± 2 , E± 2 > = - D{g(J,ň)g(S, E)g(J, 1 )g(S, E ± 1 ) F (56c)
where
f(x,y) = x ( x + l ) - y 2 ; g(x,y) = x ( x + l ) - у (y±l) (57)
It i s o b v i o u s t h a t t h e d e c o u p l i n g of t h e spin a l s o m o d i f i e s the d i a g o n a l t e r m
c o r r e s p o n d i n g t o c a s e (a) s o t h a t we obtain a r e l a t i o n m o r e c o m p l i c a t e d t h a n
(52). On t h e o t h e r h a n d , in t h e i n t e r m e d i a t e c a s e b e t w e e n (a) and (b) t h e
o f f - d i a g o n a l t e r m s s h o u l d a l s o b e t a k e n i n t o a c c o u n t by p e r t u r b a t i o n
calculation.
1.5. Perturbation calculation
In o r d e r t o d e r i v e r e l a t i o n s in a g r e e m e n t with e x p e r i m e n t f o r t h e c a s e
of m u l t i p l e t t e r m s , t h e i n t e r a c t i o n d e a l t with p r e v i o u s l y m u s t b e t a k e n into
a c c o u n t by p e r t u r b a t i o n c a l c u l a t i o n s u s i n g t h e s o l u t i o n of t h e s e p a r a t e d
w a v e e q u a t i o n a s a s t a r t i n g p o i n t . L e t us b r i e f l y c o v e r a l l t h e d e t a i l s t h a t
a r e n e e d e d i n t h e d i s c u s s i o n to f o l l o w .
(a) L e t u s denote the o p e r a t o r of t h e s e p a r a b l e wave e q u a t i o n by H 0 and

t h e o p e r a t o r of t h e p e r t u r b a t i o n t e r m s by H p , t h e n
I H - W;' I i ' > = 0 (58)
m u s t h o l d , w h e r e W' i s t h e p e r t u r b e d e n e r g y to be d e t e r m i n e d , | i * )> i s
t h e p e r t u r b e d e i g e n f u n c t i o n , and H = H 0 + H p . S i n c e H 0 i s t h e o p e r a t o r of
the s e p a r a b l e wave equation,
|H„- w j k > = 0 (59)

w h e r e | k ^ i s t h e u n p e r t u r b e d e i g e n f u n c t i o n and W k i s t h e u n p e r t u r b e d
e n e r g y . T h e p e r t u r b e d e i g e n f u n c t i o n can be w r i t t e n a s a l i n e a r c o m b i n a t i o n
of t h e u n p e r t u r b e d e i g e n f u n c t i o n s ,
|i- > Sik | k > (60)

к
S u b s t i t u t i n g (54) i n (52), m u l t i p l y i n g f r o m t h e l e f t by <JP* | and i n t e g r a t i n g ,
we o b t a i n t h e f o l l o w i n g s y s t e m of e q u a t i o n s :
(61)
к
392 K O V Á CS
where
W„ = < r l ! |H 0 | J ? > ; H{1( = (62)
F o r t h i s s y s t e m to h a v e a n o n - t r i v i a l s o l u t i o n , i t s d e t e r m i n a n t m u s t
vanish, i . e .
Wj - W ' H 12 Hi
H ,21 H,
(63)
Hr Wn - w
The s o l u t i o n Wj, . . . of t h i s s e c u l a r e q u a t i o n p r o v i d e s t h e r e q u i r e d
p e r t u r b e d e n e r g i e s . Once they a r e o b t a i n e d , t h e e l e m e n t s of the t r a n s f o r m a -
tion m a t r i x S can a l s o b e c a l c u l a t e d u s i n g f o r m u l a (61).
(b) T h e p e r t u r b a t i o n m a t r i x i s s o m e t i m e s c o m p o s e d of the p e r t u r b a t i o n
m a t r i c e s of a n u m b e r of i n t e r a c t i o n s which d i f f e r b y o r d e r s of m a g n i t u d e .
In s u c h c a s e s t h e above m e t h o d of c a l c u l a t i o n would l e a d to a p o i n t l e s s
c o m p l i c a t i o n of the f i n a l r e s u l t s . The m o s t convenient s o l u t i o n i s to s e l e c t
the g r e a t e s t of the i n t e r a c t i o n t e r m s and to s u b j e c t it to t h e above o p e r a t i o n ;
the r e m a i n d e r of the p e r t u r b a t i o n can t h e n b e t a k e n into a c c o u n t a s f o l l o w s .
L e t H = H' + H p , w h e r e H' = H 0 + H p ; H 0 i s the e n e r g y o p e r a t o r u s e d in
the f i r s t stagejDf the c a l c u l a t i o n ; H p i s t h e o p e r a t o r of t h e s t r o n g e r p e r t u r -
b a t i o n , while H p i s t h e w e a k - p e r t u r b a t i o n o p e r a t o r , to be t a k e n into account
a t a l a t e r s t a g e of the c a l c u l a t i o n . T h e n
| Н ' + H p - Wj" j i " > = 0 (64)
w h e r e W" = W;' + AW/ i s the new p e r t u r b e d e n e r g y and ji")> is the new

p e r t u r b e d e i g e n f u n c t i o n . If H p i s s m a l l , t h e n AWi' will a l s o be s m a l l , and
no g r e a t e r r o r will b e c o m m i t t e d if we r e p l a c e | i" )> by | i 1 X t h e a l r e a d y
p e r t u r b e d e i g e n f u n c t i o n of t h e o p e r a t o r H 1 . Let then, since
I H" - W) | i ' > = 0 (65)
we h a v e in a good a p p r o x i m a t i o n
| Ř p - AW/ | i ' > = 0 (66)
or
AW} = (67)
H o w e v e r , s i n c e | i ' > = ^ S j k |k)>, it f o l l o w s that

к
S
AW' = Y u k:<>|Hp| £ Sik|k> (68)
IAEA-SMR-12/ 32, 35 405
which, w r i t t e n e x p l i c i t l y , y i e l d s the following s y s t e m :
AW- =S& ( S í l H P 1 + S í 2 H P 2 + . . . . +S i n <)
+
S!i2 (Sil H21 + S i2 H22+ . . . • + S in H2n)
(69)
T a k e n into a c c o u n t in t h i s way, t h e weak i n t e r a c t i o n s c o n t r i b u t e additively

to t h e s t r o n g p e r t u r b a t i o n a l r e a d y a l l o w e d f o r . H e n c e , t h e y do not m o d i f y
the f o r m u l a s a l r e a d y e s t a b l i s h e d and t h e d e v i a t i o n s s t e m m i n g f r o m t h e m
can be r e a d i l y s e p a r a t e d f r o m the f i r s t p e r t u r b a t i o n . T h i s i s the c a s e , f o r
e x a m p l e , with the u s u a l l y s t r o n g s p i n - o r b i t i n t e r a c t i o n , on the one h a n d , and
the u s u a l l y w e a k e r s p i n - s p i n and r o t a t i o n - s p i n i n t e r a c t i o n s , o r the i n t e r a c t i o n
a r i s i n g f r o m t h e c e n t r i f u g a l t e r m , on t h e o t h e r .
2. M U L T I P L E T TERM FORMULAS
T h e m u l t i p l i c a t i o n of t h e t e r m s can b e due to two r e a s o n s ; e i t h e r the

d i f f e r e n t o r i e n t a t i o n s of the r e s u l t a n t s p i n m o m e n t u m S of t h e m o l e c u l e
i n v o l v e d i f f e r e n t e n e r g i e s , o r t h e o r i e n t a t i o n s of t h e r e s u l t a n t o r b i t a l a n g u l a r
m o m e n t u m L of t h e m o l e c u l e a r e d i f f e r e n t .
In the f i r s t c a s e we can s p e a k of S - o r s pin- m u l t i p l e t s, and in t h e
s e c o n d c a s e of L - m u l t i p l e t s . In t h e f i r s t c a s e , a c c o r d i n g to t h e coupling of
t h e s p i n m o m e n t u m to t h e i n t e r n u c l e a r a x i s o r to t h e a x i s of r o t a t i o n , we
r e f e r to H u n d ' s c a s e (a) o r (b). In t h e s e c o n d c a s e , a c c o r d i n g to t h e
coupling of the o r b i t a l a n g u l a r m o m e n t u m to the i n t e r n u c l e a r a x i s o r to the
a x i s of r o t a t i o n , we s p e a k of H u n d ' s c a s e s (a), (b) o r (d). T h e e n e r g y
e x p r e s s i o n s c o r r e s p o n d i n g to the a b o v e - m e n t i o n e d l i m i t i n g c a s e s , h o w e v e r ,
s e l d o m y i e l d v a l u e s in a g r e e m e n t with e x p e r i m e n t . T h i s i s u n d e r s t a n d a b l e
a s t h e s e l i m i t i n g c a s e s p r a c t i c a l l y m e a n n e g l e c t i n g a l l i n t e r a c t i o n s except
a f e w . In t h e r e a l m o l e c u l e , h o w e v e r , a l l i n t e r a c t i o n s a r e o p e r a t i v e to a
g r e a t e r o r l e s s e r e x t e n t . N e v e r t h e l e s s , r e s u l t s c o m p a t i b l e with e x p e r i m e n -
t a l f i n d i n g s can be o b t a i n e d if t h e s e e n e r g y v a l u e s a r e u s e d initially, i . e .
a s t h o s e of the u n p e r t u r b e d s y s t e m , and t h e o f f - d i a g o n a l m a t r i x e l e m e n t s
of a l l i n t e r a c t i o n s t r e a t e d in p r e v i o u s d i s c u s s i o n s a r e t a k e n into c o n s i d e r a t i o n
by p e r t u r b a t i o n c a l c u l a t i o n . In t h i s way we o b t a i n e n e r g i e s o r t e r m v a l u e s
i n t e r m e d i a t e b e t w e e n H u n d ' s l i m i t i n g c a s e s . F o r b r e v i t y , it i s not p o s s i b l e
h e r e to t r e a t in d e t a i l t h e s p i n - and L - m u l t i p l e t s . So we s h a l l d e a l only with
a s i m p l e e x a m p l e of s p i n - m u l t i p l e t s : t h a t of the doublet t e r m s .
2.1. Doublet t e r m s
2.1.1. Spin splitting
In the c a s e of doublet t e r m s f o r the i n t e r m e d i a t e c a s e b e t w e e n H u n d ' s

c a s e s (a) and (b) t h e p e r t u r b a t i o n t h e o r y (63) y i e l d s t h e s e c o n d - o r d e r s e c u l a r
equation
П = Л - 2 12
= 0 (70)
U = Л + i
394 K O V Á CS
w h e r e , f r o m (20), (27a), (45) a n d (40),
T ° = vn - è A A + В [ J 2 + Л]
/0 + I А Л + В | j J - Л |
I ° 2 ="H2 1» = B J a ;
HП2 J2=(J + Í)2-A2 (122)
T h e s o l u t i o n of E q . ( 7 0 ) i s
T
M (J) = "o * B J2 - è Л 2 (Y-2) 2 + 4 J;
r
l ( J ) = "o + В T2 ++ 2i Л2(Y-2)2 + 4 J 2 (72)
J+ л
w h e r e Y = А / В . Owing t o the o p p o s i t e s y m m e t r y of t h e w a v e f u n c t i o n , i n
t h e c a s e of A> 0 two i d e n t i c a l s e c u l a r d e t e r m i n a n t s a r e o b t a i n e d . T h e
energy v a l u e s will t h e r e f o r e be two-fold d e g e n e r a t e .
M a k i n g u s e of (72), the e l e m e n t s of t h e t r a n s f o r m a t i o n m a t r i x c a n a l s o
b e o b t a i n e d f r o m (61) a s
J
A
3
_ u- (J)
A+ i J - |
NÍČHJ) •J 2C" (J)
^ JA U+ (J) (73)
SA-4 .J + i =
Э
Л + 1, JÍ
•Jc^J) •J 2 C + ( J )
where
u* (J) = [ A 2 ( Y - 2 ) 2 + 4 J A ] * ± A ( Y - 2 )
C* (J) = i [ u * ( J ) 2 + 4 J 2 ] (74)
In t h e a p p l i c a t i o n of (72) we h a v e t o a d d s o m e c o r r e c t i o n t e r m s .
A m o n g t h e s e t e r m s , the c e n t r i f u g a l t e r m s h o u l d b e m e n t i o n e d f i r s t . T h e
e x p l i c i t f o r m of t h e c e n t r i f u g a l t e r m f o r t h e i n t e r m e d i a t e c a s e b e t w e e n
H u n d ' s c a s e s (a) a n d (b), a s d e r i v e d f r o m ( 5 6 a , b ) , (69) a n d (73), w i l l b e
2 2 2 2 2 2
К (J) = - D J (J a +1) + A + 2 A J ( S 4 i N - S + i N ) + 4 S A + i N S A . i N J ® (75)
W h e n s u b s t i t u t i n g J - 1 / 2 o r J + 1 / 2 f o r N , e x p r e s s i o n (75) m u s t b e a d d e d
t o (72).
A. f u r t h e r c o r r e c t i o n a r i s e s f r o m t h e i n t e r a c t i o n b e t w e e n r o t a t i o n and
s p i n . F r o m (73) a n d ( 3 1 a , b ) , (69) w e o b t a i n f o r the i n t e r m e d i a t e c a s e
H
N*( J ) " ~2~ ' 2 S A+i,N S A-|,N J A + 1] (76)
A f t e r the s u b s t i t u t i o n of J - 1 / 2 and J + 1 / 2 f o r N, E q . ( 7 6 ) m u s t b e a d d e d
t o (72). A c c o r d i n g l y , t h e f u l l - t e r m f o r m u l a f o r doublet t e r m s in the i n t e r -
m e d i a t e c a s e b e t w e e n H u n d ' s c a s e s (a) a n d (b) will be
IAEA- S M R - 1 2 / 4 2407 395
VJ) = t
n(j) + i
^(j) + h
N(j) (77)
where N = J - 1/2, J + 1/2.

0 2
^ E - t e r m s . T h e f o r m u l a v a l i d f o r E - t e r m s can be o b t a i n e d f r o m (77) by
putting Л = 0 a n d Y = 0. T h e n
F
j-t (N) F (N) = v0 + B Z N ( N + 1 ) - D £ N 2 ( N + l ) 2 + I 7 N
FJ + i (N) = F 2 (N) = v0 + B e N ( N + 1 ) - D e N 2 ( N + 1 ) 2 - | 7 ( N + l ) (78)
Many a p p l i c a t i o n s of the above f o r m u l a can b e found, f o r i n s t a n c e in

Mulliken and C h r i s t y ( F i g . 6) ( P h y s . R e v . 38, (1931) 87).
2
n - t e r m s . In m o s t c a s e s the q u a n t i t i e s D and 7 a r e so s m a l l that t h e
d e v i a t i o n s c a u s e d by t h e m a r e o b s e r v a b l e only at h i g h e r r o t a t i o n a l q u a n t u m
n u m b e r s . In s u c h c a s e s , h o w e v e r , the t e r m s 2П (and 2 Д) g e n e r a l l y f a l l
c l o s e to c a s e (b), so t h a t t h e s i m p l e c a s e - ( b ) - a p p r o x i m a t i o n of the following
c o r r e c t i o n t e r m s (putting Y = 0 in (75) and (76)) p r o v e s a d e q u a t e :
2
H" - D [ N ( N + 1) - A l (79a)
A
H f = Í 7 J ( J + 1 ) - N(N + 1)- 3/4 (79b)
N (N+ 1 ) _
F o r the 2П t e r m s K o v á c s and V u j i s i c ( J . P h y s . B . 4 , (1971) 1123).

d e r i v e d m o r e a c c u r a t e f o r m u l a s by taking into a c c o u n t a l s o the c e n t r i f u g a l
c o r r e c t i o n f o r s p i n - o r b i t a n d s p i n - r o t a t i o n i n t e r a c t i o n s ( s e e F i g . 7).
Ë 5.0
FIG. 6. Doublet splitting at the 'L, v = 0 level of CdH, according to Mulliken and Christy, y = 0. 59 c m "
pobs pcalc
- ü ü W ooo""ynnn Q oo<>ün?QiL_i:
105 J 20.5 °
,-obs _CQ[C ( b)
•Cr
10.5 20.5 О
J
FIG. 7. Deviation between observed and calculated values for the 2П state of SnH. (a) for substate F^
(b) for substate F 2 .
396 K O V Á CS
2.1.2. Л - t y p e doubling
In the c a s e Л > 0, a l l t e r m v a l u e s in (77) a r e t w o - f o l d d e g e n e r a t e . In

the c a s e of 2 n t e r m s , h o w e v e r , t h e o t h e r w i s e coincident s t a t e s a r e split up
owing to p e r t u r b a t i o n by the 2 £ t e r m s ; the r e s u l t is a Л - t y p e doublet.
A c c o u n t i n g f o r the t e r m s n e g l e c t e d on the s e p a r a t i o n of the wave equation
(41) a n d a l s o f o r t h e s p i n - o r b i t i n t e r a c t i o n (27b), p e r t u r b a t i o n c a l c u l a t i o n
(63) l e a d s to two s e c u l a r e q u a t i o n s ,
11
3/2 T^ T H° H
12 13
2
П
11
1/2
H
21 T° - T H
23 = 0 (80)
2
E H
31 H
32 T3 - T
J ± 1/2
where
T3 = v + B £ ( J + | ) (J + 3 / 2 ) ; T3" = v + B 2 ( J - l ) (J + i )
H+3 = f + 2 n ( J + 3 / 2 ) ; H23 = 5 - 2 RJ ( J - 2)
H 1 3 = - 2 r h / ( J - i ) (J + 3 / 2 ) ; rj = (B L e ) (2П; 2 Г); f = (А Ц ) (2П2£) (81 )
T h e o t h e r e l e m e n t s a r e the s a m e as in (70). The t r a n s f o r m a t i o n into

diagonal f o r m of t h e s u b - m a t r i x in t h e box in (80) y i e l d s ,
T
l - 0
"j-1/2
0 T2 - T = о (82)
^ J +1/2
T, , H H 32 T T
I ±1/2 31 ť -
where
T J H = S H + S
3 Î3 3/2,j-i l 3 i/2,J-Í 4 *
H Í23' ~= °S3 / 2 , J+i H

13 +
®l/2, J + i n 2 3
(83)
and the e x p l i c i t f o r m s of T 2 a n d T 2 a r e t a k e n f r o m (72). D i s r e g a r d i n g the

v a l u e of the spin doublet, (82) y i e l d s t h e following f i r s t a p p r o x i m a t i o n f o r
the Л - s p l i t t i n g :
A " ( % ) = 2 ( J + £ ) T S L, N F C l + c2> + S
i N S 3 / 2 , N C 2 ^ ( J - *) ( J + 3 / 2 ) ] (84)
where N = J - 1 /2, J + l / 2 . Furthermore
-1) [gir +
Cj = 2
I * v
IAEA-SMR-12/32,35 397
w h e r e E = 0 o r 1, a c c o r d i n g to t h e s y m m e t r y p r o p e r t i e s of the 2 E - t e r m
( 2 Г + о г 2 E"). T h i s f o r m u l a i s c o n f i r m e d by n u m e r o u s e x p e r i m e n t a l o b s e r -
vations (see F i g . 8 ) .
S i m i l a r l y , applying the g e n e r a l t h e o r y , the m u l t i p l e t f o r m u l a s and
Л - t y p e doublings of t h e h i g h e r m u l t i p l i c i t y t e r m s can be c a l c u l a t e d (see [ 5 ] ) .
FIG. 8. Л-type doubling of one of the 2 n-terms of ZnH (Mulliken and Christy). In Eq. (84) of the theoretical
curve. Q - 0.138 c m - 1 , Q = 0. 004 c m - 1 .
3. P E R T U R B A T I O N IN THE S P E C T R A ,
At c e r t a i n p o i n t s , t h e f r e q u e n c y a n d i n t e n s i t y d i s t r i b u t i o n s in t h e s p e c t r a
of s o m e m o l e c u l e s s u b s t a n t i a l l y d e v i a t e f r o m t h e r e g u l a r o n e s d i s c u s s e d
previously. These deviations towards i n c r e a s i n g rotational quantum n u m b e r s
r e a c h a m a x i m u m but s u d d e n l y change t h e i r sign a n d show a d e c r e a s i n g
t e n d e n c y f r o m then on, so that t h e l i n e s slowly get b a c k into t h e i r e x p e c t e d
p o s i t i o n s . Deviation l i n e s a l s o exhibit an i n t e n s i t y d e c r e a s e . T h i s pheno-
m e n o n i s c a l l e d p e r t u r b a t i o n in t h e s p e c t r o s c o p i c s e n s e .
In o t h e r c a s e s in e m i s s i o n s p e c t r a , t h e b a n d s b r e a k off e n t i r e l y , e v e n
though t h e y should continue a c c o r d i n g to t h e i n t e n s i t y d i s t r i b u t i o n l a w . On
the o t h e r hand, t h e s a m e b a n d s continue in a b s o r p t i o n s p e c t r a e v e n a f t e r
h a v i n g r e a c h e d the u p p e r v a l u e of the r o t a t i o n a l q u a n t u m n u m b e r , but the
l i n e s b e c o m e b l u r r e d and d i f f u s e . T h i s p h e n o m e n o n i s c a l l e d p r é d i s s o c i a t i o n .
In such c a s e s , we can a l w a y s find c l o s e - b y a t e r m belonging to a n o t h e r
(or the s a m e ) e l e c t r o n i c s t a t e h a v i n g t h e s a m e height a s the p r e v i o u s t e r m ,
which i n t e r a c t s with t h e p e r t u r b e d t e r m u n d e r c o n s i d e r a t i o n . H e n c e , f o r a
t h e o r e t i c a l i n t e r p r e t a t i o n of t h e o b s e r v e d p h e n o m e n a we h a v e to t u r n o u r
a t t e n t i o n to the study of p e r t u r b a t i o n s a m o n g m o l e c u l a r t e r m s .
3.1. G e n e r a l t h e o r y of p e r t u r b a t i o n s
T h e e x p e r i m e n t a l s p e c t r o s c o p i s t m e a n s by " o b s e r v e d p e r t u r b a t i o n s "
not the d e v i a t i o n s f r o m the e n e r g i e s f u r n i s h e d by t h e s e p a r a b l e wave
e q u a t i o n , but the d e v i a t i o n s f r o m the s m o o t h c o u r s e of t h e m u l t i p l e t f o r m u l a s
o b t a i n e d a f t e r having t a k e n into a c c o u n t t h e p e r t u r b a t i o n s a m o n g the d i f f e r e n t
c o m p o n e n t s of the s a m e e l e c t r o n i c s t a t e . It i s t h e s e which a r e c a l l e d
p e r t u r b a t i o n s in t h e s p e c t r o s c o p i c a l s e n s e . It b e c o m e s evident that in our
a c t u a l study of t h e s e p e r t u r b a t i o n s we should f i r s t c a r r y out t h e p e r t u r b a t i o n
c a l c u l a t i o n a m o n g the c o m p o n e n t s of t h e m u l t i p l e t t e r m u n d e r c o n s i d e r a t i o n .
T h e e n e r g i e s u n p e r t u r b e d f r o m t h e s p e c t r o s c o p i s t ' s point of view will then
b e the diagonal e l e m e n t s , i . e . t h e c a l c u l a t e d m u l t i p l e t - t e r m f o r m u l a s , and
the p e r t u r b a t i o n - m a t r i x e l e m e n t s a r e o b t a i n e d a s l i n e a r c o m b i n a t i o n s of t h e
p e r t u r b a t i o n - m a t r i x e l e m e n t s which r e s u l t f r o m t h e s e p a r a t i o n of the wave
e q u a t i o n ( s e e , f o r i n s t a n c e , E q . (73)). T h e c o e f f i c i e n t s of t h e l i n e a r
398 KOVÁ CS
c o m b i n a t i o n s a r e the t r a n s f o r m a t i o n m a t r i x e l e m e n t s f o r e a c h of the m u l t i -
p l e t s . F o r t h i s r e a s o n we c a n l i m i t o u r a t t e n t i o n to the m a t r i x e l e m e n t
o b t a i n e d on t h e s e p a r a t i o n of the wave equation, even if we want to e x a m i n e
in f u l l g e n e r a l i t y the s e l e c t i o n r u l e s g o v e r n i n g the p e r t u r b a t i o n s in t h e
s p e c t r o s c o p i c a l s e n s e , i . e . t h e r u l e s d e c i d i n g w h e t h e r o r not p e r t u r b a t i o n
i s p o s s i b l e b e t w e e n two given t e r m s . It w a s K r o n i g [ 7] who f i r s t f o r m u l a t e d
selection rules relating to these matrix e l e m e n t s .
A c c o r d i n g to the s e l e c t i o n r u l e s f o r p e r t u r b a t i o n to a r i s e b e t w e e n two
s t a t e s , t h e following c o n d i t i o n s m u s t b e s a t i s f i e d :
(1) Both s t a t e s m u s t have the s a m e rotational quantum number J,

i . e . AJ = 0.
(2) T h e r e s u l t a n t s p i n S of the two s t a t e s can d i f f e r only by 0 o r ± 1 ,
i . e . AS = 0, ± 1 .
(3) T h e c o m p o n e n t s a l o n g t h e m o l e c u l a r a x i s of the r e s u l t a n t o r b i t a l
a n g u l a r m o m e n t a of the two s t a t e s can d i f f e r only by 0 o r ± 1,
i . e . AA= 0, ± 1 .
(4) Both s t a t e s show the s a m e s y m m e t r y , i . e . both a r e e i t h e r p o s i t i v e
o r n e g a t i v e ; in the c a s e of i d e n t i c a l n u c l e i , both s t a t e s a r e e i t h e r
symmetric or antisymmetric.
S e l e c t i o n r u l e (1) i s of g e n e r a l v a l i d i t y . In H u n d ' s c a s e (b), a f u r t h e r
s e l e c t i o n r u l e AN = 0, ± 1 a l s o h o l d s . In H u n d ' s c a s e (a), b e s i d e s s e l e c t i o n
r u l e (2), the following f u r t h e r s e l e c t i o n r u l e s a p p l y : ДЕ = 0, ± 1 and
ДГ2 = 0, ± 1 .
S e l e c t i o n r u l e (3) i s equally valid f o r c a s e s (a) and (b) a s w e l l a s f o r the
i n t e r m e d i a t e c a s e , p r o v i d e d A i s defined. T h e s i t u a t i o n c h a n g e s , h o w e v e r ,
-if t h e s p i n - o r b i t i n t e r a c t i o n i s so much e n h a n c e d that the i n t e r a c t i o n b e t w e e n
L a n d 3 b e c o m e s s t r o n g e r t h a n t h e i n t e r a c t i o n of t h e s e v e c t o r s with the
i n t e r n u c l e a r axis; t h i s m a y b e o b s e r v e d e s p e c i a l l y in heavy m o l e c u l e s . In
s u c h a c a s e , A and E a r e no l o n g e r defined; only t h e i r s u m ft i s , s i n c e in
t h i s c a s e f i r s t the v e c t o r s L and В f o r m t h e r e s u l t a n t which i s coupled to
t h e i n t e r n u c l e a r a x i s by t h e component Q . It i s t h e n the e l e c t r o n i c a n g u l a r
m o m e n t u m Ó a n d the a n g u l a r m o m e n t u m of n u c l e a r r o t a t i o n R that c o m p o s e
the r e s u l t a n t J , a s in H u n d ' s c a s e (a). T h i s type of coupling i s c a l l e d H u n d ' s
c a s e (c) ( F i g . 9 ) . T h e c l a s s i f i c a t i o n of the m o l e c u l a r t e r m s l o s e s i t s
m e a n i n g h e r e , so that o n e cannot speak of E, П, Д , . . . t e r m s ; i n s t e a d ,
t h e t e r m s c a n b e c l a s s i f i e d only a c c o r d i n g to the r e s u l t a n t v a l u e i l .
s
FIG. 9. Vector model of Hundls case (c).
IAEA-SMR-12/32,35 399
T h e e i g e n f u n c t i o n s b e l o n g i n g to t h e s e s t a t e s will b e l i n e a r c o m b i n a t i o n s
of the s t a t e s of the s a m e ft:
S
Ф\ = £ S ikt /, k = Ç Y i k $ k ) Rv u J.a (86)
w h e r e s u m m a t i o n in the p a r e n t h e s e s i s to be e x t e n d e d o v e r all s t a t e s f o r
which Aft = О, Л Л = - Д Г = 0, ± 1 and AS = 0, ± 1.
T h e m a t r i x e l e m e n t s now d e s c r i b e i n t e r a c t i o n s a m o n g t h e s e s t a t e s ,
c h a r a c t e r i z e d e x c l u s i v e l y by ft i n s t e a d of Л and F,. F o r t h e s e i n t e r a c t i o n s ,
the s e l e c t i o n r u l e Aft = 0, ± 1 now r e p l a c e s А Л = 0, ± 1 .
T h e c o e f f i c i e n t s S i k in (86) a r e a l l of the s a m e o r d e r of m a g n i t u d e in
H u n d ' s c a s e (c). In the a c t u a l c a s e s s u b j e c t e d so f a r to a c l o s e t h e o r e t i c a l
s c r u t i n y , h o w e v e r , no c a s e (c) s t a t e s have b e e n e n c o u n t e r e d , but only s t a t e s
b e l o n g i n g to H u n d ' s c a s e s (a) o r (b) o r to t h e i n t e r m e d i a t e c a s e b e t w e e n
t h e m , with, at m o s t , the s i g n s of an incipient d e v i a t i o n t o w a r d s H u n d ' s
c a s e (c). T h e n the v a l u e of Эц i s n e a r l y e q u a l to unity in e x p r e s s i o n (86),
and t h a t of t h e S; k i s m u c h l e s s than unity. In the c a l c u l a t i o n of t h e m a t r i x
e l e m e n t s , h a v i n g n e g l e c t e d t h e t e r m s with c o e f f i c i e n t s that a r e t h e p r o d u c t s
of q u a n t i t i e s m u c h l e s s than unity, we obtain the o r i g i n a l m a t r i x e l e m e n t s
c o m p l e m e n t e d by s o m e t e r m s m u c h l e s s t h a n u n i t y . On t h e o t h e r hand,
t e r m s of t h i s o r d e r of m a g n i t u d e will a p p e a r a l s o in p l a c e s w h e r e t h e r e is
no i n t e r a c t i o n o t h e r w i s e . E x p e r i m e n t s have shown that t h e s e e f f e c t s cannot
be n e g l e c t e d in e v e r y c a s e .
C o n c e r n i n g t h e s e l e c t i o n r u l e (4), let us note that a r o t a t i o n a l l e v e l is
c a l l e d p o s i t i v e o r negative a c c o r d i n g to w h e t h e r the c o r r e s p o n d i n g e i g e n -
f u n c t i o n d o e s o r does not change sign upon r e f l e c t i o n at t h e o r i g i n . S i m i l a r l y ,
in t h e c a s e of i d e n t i c a l n u c l e i , t h e e x c h a n g e of the n u c l e i r e s u l t s in f u r t h e r
s y m m e t r y p r o p e r t i e s ; a s t a t e can b e s y m m e t r i c o r a n t i s y m m e t r i c depending
on w h e t h e r o r not the e i g e n f u n c t i o n of the s t a t e in q u e s t i o n c h a n g e s sign
upon s u c h an e x c h a n g e .
T h e s e s e l e c t i o n r u l e s a r e the conditions n e c e s s a r y f o r the o c c u r r e n c e
of p e r t u r b a t i o n s . T h e r e a r e c a s e s , h o w e v e r , when a l l t h e s e conditions a r e
f u l f i l l e d and yet no p e r t u r b a t i o n i s o b s e r v e d . If the o v e r l a p i n t e g r a l r e l a t i n g
to the v i b r a t i o n a l p a r t of the e i g e n f u n c t i o n d i s a p p e a r s , i . e . , if t h e r e i s no
such i n t e r n u c l e a r - d i s t a n c e v a l u e r f o r which the two v i b r a t i o n a l e i g e n f u n c t i o n s
a r e s i m u l t a n e o u s l y n o n - z e r o , then no p e r t u r b a t i o n o c c u r s even if the a b o v e -
m e n t i o n e d conditions a r e f u l f i l l e d ( F r a n k - C o n d o n p r i n c i p l e ) .
3.1.1. P e r t u r b a t i o n of two d i s c r e t e s t a t e s
H e r e t h e p e r t u r b e d e n e r g i e s can b e c a l c u l a t e d f r o m a s e c u l a r e q u a t i o n
of s e c o n d d e g r e e which i s the f u n c t i o n of the r o t a t i o n a l q u a n t u m n u m b e r .
Its s o l u t i o n i s
w h e r e W A a n d WB m e a n t h e u n p e r t u r b e d e n e r g i e s in t h e s p e c t r o s c o p i c a l
s e n s e and H A B i s the p e r t u r b a t i o n m a t r i x e l e m e n t b e t w e e n the two s t a t e s
concerned.
400 K O V Á CS
If E q . (87) i s w r i t t e n in t h e f o r m
WB - WA I /WA - W \2 ~ ~
W l = WA + - +\l( 2 J + |HAB|
W
B - W
A / / W , - W. \2 "
W = W
2 B - - 4 \ ) + |HAB I2 <88>
t h e n it can b e s e e n that the two s t a t e s a r e s h i f t e d a p a r t to a d i s t a n c e of

equal m a g n i t u d e but of o p p o s i t e sign, i . e . , it s e e m s a s if the c o r r e s p o n d i n g
l e v e l s r e p e l e a c h o t h e r ( F i g . 10).
FIG. 10. The solid lines represent the perturbed energies, the dashed lines represent the energies for the
hypothetical case of no interaction between the two states, and the dash-dot lines show the arithmetic mean,
not influenced by perturbation, of the solid curves [ 5 ] .
Since g e n e r a l l y only one of the two u n p e r t u r b e d s t a t e s in q u e s t i o n

c o n t r i b u t e s to the p r o d u c t i o n of the s p e c t r a l l i n e s , it i s usually the c o n t r i -
buting s t a t e that i s c a l l e d u n p e r t u r b e d (or p e r t u r b e d in t h e neighbourhood
of the point of p e r t u r b a t i o n ) , w h e r e a s the o t h e r one i s called t h e p e r t u r b i n g
s t a t e . L e t us denote the f i r s t state by WA and t h e second by WB and let us
i n t r o d u c e t h e d i f f e r e n c e b e t w e e n the p e r t u r b e d and u n p e r t u r b e d s t a t e s a s
follows:
W W W W
л W B - A
A 2a= w2 - wA = ^; V B - A ^ , |
J + IHA g| 2I
T T
W W W W
B - A I i A - B V + ,H ,2
Aia=wI-Wa 2 J I ABI (89)
T h e s e v a l u e s have b e e n plotted v e r s u s J in F i g . 11.

We s e e f r o m F i g . 11 that the deviations i n c r e a s e with i n c r e a s i n g
r o t a t i o n a l q u a n t u m n u m b e r up to a d e f i n i t e point, w h e r e they suddenly change
sign and d e c r e a s e g r a d u a l l y f r o m t h e r e o n . T h i s r e s u l t s in a s i m i l a r
s h i f t i n g of t h e s p e c t r a l l i n e s a s s o c i a t e d with t h e s e t e r m s . T h e t h e o r e t i c a l
r e s u l t s just m e n t i o n e d a r e in e x c e l l e n t a g r e e m e n t with t h e e x p e r i m e n t a l
results.
IAEA-SMR-12/32,35 401
FIG. 11. Difference between the perturbed and unperturbed terms vs. the rotational quantum number [ 5 ] .
T h e e i g e n f u n c t i o n s b e l o n g i n g to t h e two p e r t u r b e d s t a t e s c a n b e
written as
= S + S
1AÂ 1B^B
5 + S (90)
2AÂ 2B^B
w h e r e t h e c o e f f i c i e n t s c a n b e c a l c u l a t e d f r o m E q . ( 6 1 ) . B y m e a n s of the
p e r t u r b e d e i g e n f u n c t i o n s w e c a n c a l c u l a t e the i n t e n s i t i e s of the p e r t u r b e d
l i n e s . In t h e p r e s e n c e of p e r t u r b a t i o n , t h e v e c t o r of t h e e l e c t r i c m o m e n t
will b e c o m e
R 1 D =/^M0 D dT = SlARAD+SlBRBD
R
2D = / ^ ^ D d T = S2ARAD+S2BRBD (91)
w h e r e IjjD i s t h e e i g e n f u n c t i o n of t h e l o w e r s t a t e of the t r a n s i t i o n a n d RAD

a n d RgQ a r e the v e c t o r s of the e l e c t r i c m o m e n t of t h e t r a n s i t i o n t o t h e D
t e r m f r o m t h e A a n d В t e r m s , r e s p e c t i v e l y . We f i n d f r o m E q . (91) t h a t t h e
i n t e n s i t i e s a r e p r o p o r t i o n a l to the e x p r e s s i o n
I ID ~ S 21A IAD + S IB
2
I BD + 2 S 1A S IB I AB
^ L A D + ^ B D + ^ A ^ A B (92)
w h e r e I A D = |I R A d | 12, I B D = i| R (2
BD I > ANC^ I AB r e a
l p a r t of t h e e x p r e s s i o n
R | d R b d . Since in g e n e r a l t h e r e i s no s i m u l t a n e o u s t r a n s i t i o n f r o m the
p e r t u r b i n g a n d p e r t u r b e d s t a t e s to t h e s a m e D t e r m , s u c h t r a n s i t i o n s b e i n g
r e s t r i c t e d to t h e p e r t u r b e d s t a t e , I ß D a n d I A B c a n b e t a k e n to b e z e r o . T h e n
T ~ Ч2 T
ID 1A AD
V ^ L ^ A d (93)
2 2
If S B a n d S a a r e e x p r e s s e d b y t h e p e r t u r b a t i o n d e v i a t i o n s i n t r o d u c e d in (89),
t h e n E q . (93) w i l l a s s u m e t h e f o r m
*1D 1Д2А1
— = 1Д-Т (94)
1
2D I 1A
402 K O V Á CS
C o n s e q u e n t l y , the i n t e n s i t i e s a r e i n v e r s e l y p r o p o r t i o n a l to the p e r t u r b a t i o n
d e v i a t i o n s of t h e l i n e s , i . e . t h e line u n d e r g o i n g the g r e a t e r s h i f t will be
p r o p o r t i o n a t e l y w e a k e r , and v i c e v e r s a . T h e s e r e s u l t s a r e a l s o in e x c e l l e n t
a g r e e m e n t with e x p e r i m e n t .
Since s u c h a d j a c e n t t e r m s will a f f e c t one a n o t h e r , t h e y f r e q u e n t l y b e a r
m e s s a g e s of m o l e c u l a r s t a t e s that could not b e d e t e c t e d o t h e r w i s e . M o r e -
o v e r , in a d d i t i o n t o t h e kind of t h e p e r t u r b i n g t e r m s , it i s p o s s i b l e to
d e t e r m i n e a l s o t h e i r c h a r a c t e r i s t i c c o n s t a n t s , w h e r e b y the study of
p e r t u r b a t i o n s s i g n i f i c a n t l y c o n t r i b u t e s to o u r u n d e r s t a n d i n g of m o l e c u l a r
structures.
3.1.2. P e r t u r b a t i o n of a d i s c r e t e and a continuous s t a t e ; predissociation
So f a r we h a v e a s s u m e d t h a t the s t a t e s i n t e r a c t i n g with e a c h o t h e r a r e
all d i s c r e t e s t a t e s . T h e r u l e s extend, h o w e v e r , a l s o to all t h o s e c a s e s
w h e r e one (or all) of the t e r m s p a r t i c i p a t i n g in the p e r t u r b a t i o n b e l o n g to a
c o n t i n u o u s s t a t e . In t h e i n t e r a c t i o n of a continuous s t a t e with a d i s c r e t e
s t a t e , the l a t t e r i s not s h i f t e d but m a y , with a c e r t a i n n o n - z e r o p r o b a b i l i t y ,
go o v e r to t h e f o r m e r (without r a d i a t i o n ) l e a d i n g to the d e c o m p o s i t i o n of
the m o l e c u l e . T h i s i s t h e phenomenon c a l l e d p r e d i s s o c i a t i o n ( s e e F i g . 12).
FIG. 12. Interpretation of predissociation in the bands. When the rotational levels of term A reach the
height of the continuous part of term C, the bands of A become diffuse [ 5 ] .
At t h e s a m e t i m e t h e r e i s a finite p r o b a b i l i t y t h a t , b e f o r e t h i s p r e -
d i s s o c i a t i o n o c c u r s , thé m o l e c u l e g o e s o v e r to a l o w e r s t a t e while e m i t t i n g
r a d i a t i o n , i . e . giving r i s e to a s p e c t r a l l i n e . To study t h e s e r e l a t i o n s •
q u a n t i t a t i v e l y , it i s a d v i s a b l e to take into a c c o u n t a l s o t h e i n t e r a c t i o n
b e t w e e n the m o l e c u l e and t h e r a d i a t i o n f i e l d . T h e s t a t e s of the s y s t e m
c o m p o s e d of the m o l e c u l e p l u s t h e r a d i a t i o n f i e l d can be d e s c r i b e d , a c c o r d i n g
to D i r a c , by the n o r m a l i z e d e i g e n f u n c t i o n
| N V N 2 , . . . , N p , . . . , q 2 , q 2 , . . . , t >; / I I > I =1 (95)
w h e r e q ^ q 2 , . . . a r e t h e p o s i t i o n a l and s p i n c o - o r d i n a t e s of the e l e c t r o n and

the n u c l e i , and Nj, N 2 , . . . a r e t h e n u m b e r s of light q u a n t a in t h e f i r s t ,
s e c o n d , e t c . , m o n o c h r o m a t i c plane wave, w h o s e l i n e a r c o m b i n a t i o n
c o n s t i t u t e s the r a d i a t i o n f i e l d . Let us denote t h e e i g e n f u n c t i o n s of t h e
IAEA-SMR-12/11 403
m o l e c u l a r s t a t e s without t h e r a d i a t i o n f i e l d by 11 У (these a r e the e i g e n -

f u n c t i o n s we have dealt with so f a r ) , w h e r e f i s t h e t o t a l i t y of the q u a n t u m
n u m b e r s r e f e r r i n g to e n e r g y . T h e f o r m an o r t h o g o n a l and n o r m a l i z e d
c o m p l e t e s y s t e m , b e c a u s e they depend only on t h e p o s i t i o n a l and s p i n co-
o r d i n a t e s of the p a r t i c l e s , so we can w r i t e that
| N j . N2, . . . ; q v q 2 , . . . , t > = £ а { ( ^ , N a , . . . , t) | t > ;

!
£ l a í I2 = 1
<96)
N p ,«
w h e r e the c o e f f i c i e n t s a $ d e p e n d not only on the t i m e and t h e q u a n t u m

n u m b e r s Np of the r a d i a t i o n f i e l d , but a l s o on t h e s u m of t h e e n e r g y q u a n t u m
n u m b e r s of the p a r t i c l e s .
Let HQ denote the o p e r a t o r r e f e r r i n g t o the s e p a r a b l e p a r t of the wave
equation of the m o l e c u l e ; let G 0 denote the e n e r g y o p e r a t o r of t h e r a d i a t i o n
field; let H p be the o p e r a t o r of p e r t u r b a t i o n b e t w e e n d i f f e r e n t l e v e l s in the
m o l e c u l e ; and let G p b e the s m a l l p e r t u r b a t i o n o p e r a t o r d e s c r i b i n g the
i n t e r a c t i o n of t h e r a d i a t i o n f i e l d with t h e m o l e c u l e . The t i m e - d e p e n d e n t
wave equation w i l l then b e :
| Н 0 + С 0 + Н Р + С Р | ^ , N2 qv q2, . . . , t>
= - f I | N l ,N2, ..., q i ,q 2 , ...,t> (97)
If now the f o r m of | f r o m E q . ( 9 6 ) is s u b s t i t u t e d into (97), m u l t i p l i e d

f r o m the l e f t by <( к* | a n d i n t e g r a t e d , the wave equation w i l l a s s u m e the
form
Wk h Лр)
+
Г ak =
'ki
X (Np+lâ^Nj, ...,Np+l, . . . ) + N ^ a p t N j , . . . . N p - 1, , . . ) (98)

where
G ^ = < k* |GP ( q ť q 2 , . . . ) | Í > (99)
w h e r e GP d e n o t e s the p a r t of G p which d e p e n d s on t h e p o s i t i o n a l c o - o r d i n a t e s
r e l a t e d to t h e v e c t o r p o t e n t i a l of the p - t h plane w a v e .
T h e p r o b l e m can be r e g a r d e d a s s o l v e d when the c o e f f i c i e n t s a k have
b e e n explicitly c a l c u l a t e d f r o m (98), s i n c e (96) y i e l d s the p r o b a b i l i t i e s of
o c c u r r e n c e of the s t a t e s by | a k | 2 . If t h e s e l e c t i o n r u l e s a r e s a t i s f i e d b e t w e e n
the d i s c r e t e s t a t e A and the c o n t i n u o u s s t a t e C, then only the c o e f f i c i e n t s a k
in (98) will b e d i f f e r e n t f r o m z e r o , f o r which
J2=... = Np = = 0
Jo2 = =N = (100)
P
D, N . h = • •• = N N P+1
P-l
N = 1
p
4 0 4 KOVÁ CS
WA - WD - he < hvp < WA - W D + he (101)
Since s t a t e С i s continuous, the e i g e n f u n c t i o n w i l l now b e
I >= a k ( 0 , 0, . . . , 0 t) I A > + J a c ( Ó , 0 0 W , t ) | c > dW
+ (0, Ó, . . . , 1, . . . , t) | D > (102)
w h e r e |c^> depending on W i s the e i g e n f u n c t i o n belonging to the continuous

state.
A f t e r s u b s t i t u t i n g E q . (102) into (98) by a l i n e a r d i f f e r e n t i a l equation
s y s t e m like (98), the c o e f f i c i e n t s a k a r e o b t a i n e d a s
a , = exp ÍWA +
H V A D + VAC) (103a)
l-exp{[|(W-WA)-|(VAD+VAC)]t}
a W =
C< > ii CA( > H W exp (103b)
<n
| ( w - w a ) - l(vAD+vAC)
DA
a(P) = exp - S ( W D +
b,)t (103c)
D h
+ ( V + v
%4 è AD A c>
where
A
IG | v ) f
AD D
v = f |Hac(Wa)|2 (104)
AD •л A C
a r e the r e c i p r o c a l s of t h e a v e r a g e l i f e t i m e of s t a t e A f o r t r a n s i t i o n to
s t a t e D ( p r o v i d e d s t a t e С i s not p r e s e n t ) and f o r t r a n s i t i o n to s t a t e С
(provided s t a t e D i s not p r e s e n t ) , r e s p e c t i v e l y . N o r m a l l y V AD = Ю 8 s" 1
and V A C ^ 10 1 1 - 10 12 s" 1
T h e s e a r e the v a l u e s to b e s u b s t i t u t e d into E q . (102). Since the v a l u e s
I a k I give the p r o b a b i l i t i e s of o c c u r r e n c e of the s t a t e s |k)>, s o m e
r e a r r a n g e m e n t s of ( 1 0 3 a - c ) w i n lend t h e r e l a t i o n s
| a . | 2 = e x P [-(VAD+ VAC)t] (105a)
f [ac(W)|2dW = Г1 - exp [ - ( V A D + V A C ) t ] (105b)

J
AD AC L
l - e x p [ - ( V A D + VAC)t (105c)
f l wi'- v AD + v A C
L e t u s now e x a m i n e the m e a n i n g of (105). At t h e b e g i n n i n g of the t i m e

i n t e r v a l (t = 0) we o b t a i n f r o m (105)
IAEA-SMR-12/32,35 405
I а д I 2 = 1, J | a c ( W ) | 2 dW =J ^ f dv = 0 (106)
P
i . e . only s t a t e A i s e x c i t e d ; in o t h e r s t a t e s t h e r e a r e no m o l e c u l e s a s h a s
been assumed.
F o r the c a s e t E q . ( 1 0 5 ) g i v e s the r e s u l t s
I a A I2 = 0 _ (107a)
J |ac(W)|2dW (107b)
{107C)
f l LAWL'dv-^-^V-
J i—> AD AC
P
T h i s i s e q u i v a l e n t to s t a t i n g that with t -* t h e r e will be no m o l e c u l e s in
s t a t e A, a s they will a l l be d i s t r i b u t e d b e t w e e n s t a t e s С and D with
p r o b a b i l i t i e s given b y E q s (107b) and (107c), r e s p e c t i v e l y . Using the
n u m e r i c a l v a l u e s of V A D and У д с given above, we obtain
Г I 12 10 12
J
/ lMw)l dW =
ss 12 * 1
10 + 10 12
я aJP)
D řI „ , , =-
10 + 1 о1
8
10° -10 (108)
T h i s m e a n s t h a t , in the p r e s e n c e of a continuous s t a t e , the i n t e n s i t y

of the s p e c t r a l line i s r e d u c e d , p r o v i d e d the s e l e c t i o n r u l e s a r e f u l f i l l e d ,
to about one t e n - t h o u s a n d t h of i t s o r i g i n a l v a l u e , a n d a l m o s t a l l m o l e c u l e s
a r e t r a n s f e r r e d in a r a d i a t i o n l e s s way to t h e c o n t i n u o u s s t a t e , i . e . the
m o l e c u l e d e c o m p o s e s ( d i s s o c i a t e s ) without t h e p r e d i s s o c i a t i n g s t a t e having
r e a c h e d i t s own d i s s o c i a t i o n l i m i t . T h i s i s the e x p l a n a t i o n f o r the a b r u p t
b r e a k i n g off in the e m i s s i o n b a n d s .
A s we know f r o m H e i s e n b e r g ' s u n c e r t a i n t y r e l a t i o n , the s m a l l e r t h e
l i f e t i m e of an a t o m i c s y s t e m e m i t t i n g o r a b s o r b i n g light, t h e b r o a d e r i s the
c o r r e s p o n d i n g s p e c t r a l l i n e . Since in the p r e s e n c e of the continuous s t a t e
t h e l i f e t i m e of the u p p e r d i s c r e t e s t a t e d e c r e a s e s f r o m 10" 8 to 10" 12 s, i . e .
to a t e n - t h o u s a n d t h of i t s o r i g i n a l v a l u e , the line width of t h e c o r r e s p o n d i n g
s p e c t r a l line i n c r e a s e s by the s a m e f a c t o r . When the l i n e s a r e b r o a d
enough they o v e r l a p , so that t h e r o t a t i o n a l s t r u c t u r e d i s a p p e a r s and the band
b e c o m e s d i f f u s e . The d i f f u s e b a n d s can, however,, s t i l l be d i s t i n g u i s h e d
f r o m e a c h o t h e r s i n c e t h e b r o a d e n i n g c a l c u l a t e d above i s i n s u f f i c i e n t to
p r o d u c e o v e r l a p p i n g in the d i f f u s e b a n d s . T h e r e a s o n why the r o t a t i o n a l
s t r u c t u r e b e c o m e s d i f f u s e w h e r e a s the v i b r a t i o n a l s t r u c t u r e d o e s not, i s
that t h e l i f e t i m e of t h e m o l e c u l e i s l e s s (10" 1 2 s) than the d u r a t i o n of a
r o t a t i o n c y c l e (~ 1 0 _ 1 1 s ) , so t h a t t h e r e can b e no w e l l - d e f i n e d q u a n t i z e d
r o t a t i o n . On t h e o t h e r h a n d , t h i s l i f e t i m e is m u c h l o n g e r than the d u r a t i o n
of a v i b r a t i o n c y c l e (10~ 1 3 to 1 0" 14 s) and t h e v i b r a t i o n s t r u c t u r e i s thus
406 K O V Á CS
p r e s e r v e d . T h i s i s the explanation f o r the p r e d i s s o c i a t i o n p h e n o m e n a

o b s e r v e d in a b s o r p t i o n .
T h e o b s e r v a t i o n and s y s t e m a t i c c l a s s i f i c a t i o n of p r e d i s s o c i a t i o n
p h e n o m e n a r e n d e r s it p o s s i b l e to c o r r e l a t e the e n e r g y p a t t e r n s of the a t o m s
f o r m i n g the m o l e c u l e to the e n e r g y p a t t e r n of the m o l e c u l e i t s e l f . T h u s ,
f r o m the d e t e r m i n a t i o n of the d i s s o c i a t i o n e n e r g i e s of v a r i o u s c o m b i n a t i o n s
of a t o m s (which m a y be v e r y a c c u r a t e ) we obtain an e x p e r i m e n t a l b a s i s f o r
the study of t h e m o s t f u n d a m e n t a l p r o b l e m of c h e m i s t r y , n a m e l y the n a t u r e
of the c h e m i c a l bonds in the a s p e c t of f o r m a t i o n and d e c o m p o s i t i o n , which
cannot be s u r p a s s e d by any o t h e r m e t h o d , not excluding c h e m i c a l m e t h o d s in
the s t r i c t s e n s e e i t h e r . T h i s i s the fact which l e n d s an e x t r e m e i m p o r t a n c e
t o t h e o b s e r v a t i o n of p r e d i s s o c i a t i o n p h e n o m e n a .
4. INTENSITY DISTRIBUTION IN ROTATIONAL BANDS
4.1. G e n e r a l t h e o r y and s e l e c t i o n r u l e s
T h e s p e c t r a l l i n e s a r e c h a r a c t e r i z e d not only by t h e i r p o s i t i o n in t h e
s p e c t r u m , but a l s o by t h e i r i n t e n s i t y o r s t r e n g t h . In o t h e r w o r d s , if the
t r a n s i t i o n p r o d u c i n g the line in q u e s t i o n i s a d m i t t e d by the s e l e c t i o n r u l e s ,
the p r o b l e m that e m e r g e s i s t h e p r o b a b i l i t y of t h e t r a n s i t i o n . As is known,
t h e t r a n s i t i o n p r o b a b i l i t i e s i n t r o d u c e d by E i n s t e i n f o r s p o n t a n e o u s e m i s s i o n
and f o r a b s o r p t i o n a r e r e l a t e d to the s q u a r e of the m a t r i x e l e m e n t R of the
dipole m o m e n t of the m o l e c u l e . If it i s a s s u m e d t h a t , in a f i r s t a p p r o x i -
m a t i o n , e l e c t r o n m o t i o n and t h e v i b r a t i o n and r o t a t i o n of the n u c l e i do not
i n f l u e n c e e a c h o t h e r , t h e n the dipole m o m e n t of the m o l e c u l e can be w r i t t e n a s
Rnn',.vvl!l
J = J f Ф'*
a M^'dT
= / <Č*,R*, uS 4 ( M e + M ) ф „ R „ u „ n„ dT
J n v J ,fi , M e n' v J ,£2 , M"
= / ф* M ф R*.
v
Rv ,,u* n , ... u „ n „ .... dT
J n e n" M J ,Q , M
+ / Tф'К ф „ d T / R*. u , M R „u „,. лл „dTv v (109)

J n e j v J , fi, M n v J ,ÍJ ,M n '
w h e r e M i s t h e v e c t o r o p e r a t o r of t h e e l e c t r i c m o m e n t , which can b e
r e s o l v e d into two p a r t s : M = M e + M n . H e r e M e d o e s not depend on the
i n t e r n u c l e a r d i s t a n c e , w h e r e a s M n d e p e n d s on nothing e l s e . фа i s t h e e i g e n -
f u n c t i o n c o r r e s p o n d i n g to H u n d ' s c a s e (a), which i s o b t a i n e d a s t h e p r o d u c t
of the e i g e n f u n c t i o n s of e l e c t r o n m o t i o n and n u c l e a r v i b r a t i o n and r o t a t i o n ,
u n d e r the a s s u m p t i o n of m u t u a l i n d e p e n d e n c e of t h e s e m o t i o n s . F u r t h e r m o r e ,
dT = d î .e d î nn, w h e r e dTe i s the v o l u m e e l e m e n t of the e l e c t r o n c o - o r d i n a t e s ,
and dT n = r z sinô d 0 du dr i s the v o l u m e e l e m e n t of t h e n u c l e a r c o - o r d i n a t e s ,
Since in (109) t h e e l e c t r o n i c e i g e n f u n c t i o n s b e l o n g to d i f f e r e n t e l e c t r o n i c
s t a t e s and s i n c e they a r e m u t u a l l y o r t h o g o n a l , the s e c o n d t e r m in (109)
vanishes.
T h e s q u a r e of the r e m a i n i n g p a r t of (109) in t e r m s of i t s c o m p o n e n t s
in the s p a c e - f i x e d s y s t e m will be
IAEA-SMR-12/32,35 407
n ' v ' J*
R R„ R„ + R. (110)
I " n'VJ' Z
M'M" M'M"
R e i c h e a n d R a d e m a c h e r found that, of t h e above e x p r e s s i o n s , R x f 0,
Ryj 4 0 only if AM = ± 1, w h e r e a s R 7f 0 if AM = 0. T h i s is the f i r s t s e l e c t i o n
r u l e which, in our c a s e , m e a n s that s u m m a t i o n with r e s p e c t to M can be
n e g l e c t e d f o r e m i s s i o n , w h e r e a s that with r e s p e c t to M1 can b e n e g l e c t e d
for absorption.
F u r t h e r e x a m i n a t i o n (Landau) h a s shown that
I
n ' v ' J'
R' = 3 R„ (111)
n"v"J" I
w h e r e , f o r e m i s s i o n , M = M1 and M can v a r y f r o m - J ' to + J ' , while f o r
a b s o r p t i o n , M = M " and M can a s s u m e the v a l u e s - J " , . . . , + j " . We s e e
f r o m E q . ( I l l ) that it i s enough to study t h e c o m p o n e n t R z in t h e a b s e n c e
of an e x t e r n a l m a g n e t i c f i e l d and n e g l e c t i n g p o l a r i z a t i o n .
Since M z , e x p r e s s e d in t e r m s of i t s c o m p o n e n t s in t h e m o l e c u l e - f i x e d
s y s t e m , i s given by
M, = M л Sine + M j cos ( (112)
we h a v e
R„ = fc M,A"dTe M UJ",Í!",M i 2 e d e du
X [ф*Мпф„йт Г U* v< u„ n ,„ „Sine cos в de) rR,R„r2dr (113)

J I n e J y,Cl,M 3 Si M J J v v
Since t h e r o t a t i o n a l e i g e n f u n c t i o n s Uj a M and the c o m p o n e n t s M^,

do not depend on t h e i n t e r n u c l e a r d i s t a n c e r , and s i n c e t h e change of the
e l e c t r o n i c e i g e n f u n c t i o n s фп v e r s u s r i s u s u a l l y slow ( a f t e r a v e r a g i n g o v e r r )
the c o r r e s p o n d i n g i n t e g r a t i o n can b e c a r r i e d out b e f o r e t h e o v e r l a p
integration
2
<br - J ï W - ^ (114)
( F r a n c k - C o n d o n p r i n c i p l e ) . T h e s q u a r e of (114) i s p r o p o r t i o n a l to t h e band
s t r e n g t h . T h e i n t e g r a l s c o n n e c t e d with t h e e l e c t r o n i c e i g e n f u n c t i o n s a r e
t h e rj- and Ç- c o m p o n e n t s of the e l e c t r o n i c t r a n s i t i o n m o m e n t ,
R
"' n " =
/ К '
dT (U5)
f o r which t h e s e l e c t i o n r u l e s AE = 0, AS = 0 a r e v a l i d , s i n c e M d o e s not
depend on t h e spin, and t h e s p i n - d e p e n d e n t p a r t s of t h e e l e c t r o n i c e i g e n -
f u n c t i o n s a r e o r t h o g o n a l . The s q u a r e of (115) i s p r o p o r t i o n a l to the e l e c t r o n i c
transition probability.
T h e i n t e g r a l s r e l a t i n g to the r o t a t i o n a l c o - o r d i n a t e s in (113) can be
w r i t t e n in t h e f o r m
*
408 KOVÁ CS
J'fi'M / , COS 0
u> sin
ь,..п..лл=
J iî M J/ f. о' »x J ,п..
J.fl.M Í! ,лM, е s i n „0d ě d u (116)
A s c a n b e shown, t h e s e l e c t i o n r u l e r e l a t i n g to t h e s e i n t e g r a l s i s
AÇl = 0 , ± 1 . M o r e s p e c i f i c a l l y , ДГ2 = 0 f o r the e x p r e s s i o n having cos 0 and
Д57 = ± 1 f o r the e x p r e s s i o n having s i n 0 in the p l a c e of t h e a l t e r n a t i v e
t r i g o n o m e t r i c f u n c t i o n . Since, h o w e v e r , the p r e v i o u s l y m e n t i o n e d s e l e c t i o n
r u l e ДЕ• = 0 a l s o h o l d s , the above r e l a t i o n s a r e e q u i v a l e n t to the s e l e c t i o n
r u l e Д Л = 0, ± 1. T h i s m e a n s that, f o r any e l e c t r o n i c t r a n s i t i o n , only one
t e r m in E q . (113) can b e n o n - z e r o .
It can a l s o be shown that f o r (116) the s e l e c t i o n r u l e A J = 0, ± 1 a l s o
h o l d s . T h e s e r i e s of l i n e s c o r r e s p o n d i n g to the t r a n s i t i o n s A3 = 0 i s c a l l e d
the Q - b r a n c h , w h e r e a s t h o s e f o r which A J = -1 o r +1 a r e c a l l e d P - o r It-
branches, respectively.
S u m m i n g t h e s q u a r e of the a b s o l u t e v a l u e in (116) o v e r the p o s s i b l e
v a l u e s of t h e m a g n e t i c q u a n t u m n u m b e r a n d m u l t i p l y i n g by t h r e e , we obtain
a n e x p r e s s i o n c a l l e d line s t r e n g t h :
+J +J „
V i rr i2 i J'n'M i
s
rr =1 l R »t I = 3
L I (U7>
M=-J M=-J
in w h i c h J = J 1 f o r e m i s s i o n a n d J = j " f o r a b s o r p t i o n .
In view of the above c o n s i d e r a t i o n s we obtain f o r (110) o r (111)
R nvr i = | R n'n" I |H V ' V " I 2 S (118)

1 1 1 1
I n v J ' e vibr JJ
With
К " à
E'Z" à .
Л Л" 1 J <A"' , , M
nЛZ ф г
4 п"Л"2"dr e
Z,
+5 V a ' E' (2S + 1)" 1 (119)

Л",Л'±1'
w h e r e S = S 1 f o r e m i s s i o n and S = S" f o r a b s o r p t i o n , and the r e m a i n d e r i s

to b e t a k e n f r o m (114) and (117).
By t h e above c o n s i d e r a t i o n , the i n t e n s i t y of an e m i s s i o n line can b e
written as
c п s ex
с ; ' " - к " Г к ; : : г J T p ^
w h e r e С can be r e g a r d e d a s c o n s t a n t at a given t e m p e r a t u r e within a

p a r t i c u l a r b a n d , Fj. is the r o t a t i o n a l t e r m f o r the m u l t i p l e t c o m p o n e n t s ,
k i s t h e B o l t z m a n n c o n s t a n t , and T i s the a b s o l u t e t e m p e r a t u r e .
Since in (12 0) a l l f a c t o r s can be r e g a r d e d a s c o n s t a n t to a good a p p r o x -
i m a t i o n within a b a n d (except f o r the B o l t z m a n n f a c t o r and the line s t r e n g t h )
the i n t e n s i t i e s of the s p e c t r a l l i n e s within a b a n d depend, once t h e B o l t z m a n n
f a c t o r h a s b e e n taken c a r e of, only on the line s t r e n g t h . In o t h e r w o r d s ,
the r e l a t i v e i n t e n s i t i e s of t h e individual l i n e s of a band a r i s i n g f r o m a
IAEA-SMR-12/32,35 409
m u l t i p l e t t r a n s i t i o n a r e d e t e r m i n e d , a p a r t f r o m the B o l t z m a n n f a c t o r , by
t h e l i n e s t r e n g t h ; it i s the l a t t e r which c h a r a c t e r i z e s the i n t e n s i t y
d i s t r i b u t i o n a m o n g t h e b r a n c h e s . T h e t h e o r e t i c a l p r e d i c t i o n of t h e s e l i n e
s t r e n g t h s i s t h e r e f o r e of c o n s i d e r a b l e i m p o r t a n c e . The s u b j e c t of t h e
p r e s e n t d i s c u s s i o n i s to p r o v i d e a t h e o r e t i c a l b a s i s f o r c o m p u t i n g the line
s t r e n g t h s f o r t h e v a r i o u s p o s s i b l e t r a n s i t i o n s a d m i t t e d by t h e s e l e c t i o n
rules.
T h e i n t e n s i t y d i s t r i b u t i o n i n c l u d e s many p h e n o m e n a which will not b e
dealt with h e r e , e . g . the d e p e n d e n c e of i n t e n s i t y d i s t r i b u t i o n on e x c i t a t i o n ,
i n t e n s i t y a l t e r a t i o n s in h o m o n u c l e a r m o l e c u l e s , the i n t e n s i t y of t h e Z e e m a n
c o m p o n e n t s , and o t h e r a n o m a l i e s . F o r t h e s e s u b j e c t s , the r e a d e r i s
r e f e r r e d to the w e l l - k n o w n e x c e l l e n t book of H e r z b e r g [4] .
4.2. I n t e n s i t y d i s t r i b u t i o n a m o n g spin m u l t i p l e t s
T h e i n t e n s i t i e s o r line s t r e n g t h s , c a l c u l a t e d on t h e b a s i s of t h e p r e v i o u s
d i s c u s s i o n , a g r e e with the e x p e r i m e n t a l f i n d i n g s only if a l l t e r m s in the
t r a n s i t i o n s belong to H u n d ' s c a s e (a). T h i s i s u n d e r s t a n d a b l e a s the c a s e (a)
e i g e n f u n c t i o n s w e r e u s e d to d e r i v e o u r f o r m u l a s . Many a u t h o r s have dealt
with t h e e s t a b l i s h m e n t of line s t r e n g t h s . T h e s e e x p r e s s i o n s a r e given in
t h e i r g e n e r a l f o r m in T a b l e I.
T h e s u b s t i t u t i o n of a p p r o p r i a t e ft-values y i e l d s c a s e (a) line s t r e n g t h s
f o r t r a n s i t i o n s of any type and m u l t i p l i c i t y . In the line s t r e n g t h c o l u m n s ,
Г2 a l w a y s m e a n s t h e s m a l l e r of the two f2's i n v o l v e d in t h e t r a n s i t i o n .
Since in the c a s e of m u l t i p l e t t e r m s t h e Г - t e r m s a l w a y s b e l o n g to
c a s e (b) and m o s t of the o t h e r t e r m s b e l o n g to the i n t e r m e d i a t e c a s e , in
r i g o r o u s c a l c u l a t i o n s we m u s t u s e t h e i n t e r m e d i a t e - c a s e e i g e n f u n c t i o n s
i n s t e a d of t h e e i g e n f u n c t i o n s ф T h e y can b e e x p r e s s e d a s l i n e a r c o m b i -
n a t i o n s of t h e c a s e (a) e i g e n f u n c t i o n s :
+s
S
^N = £ A + E,N (121)
£ = -S
w h e r e the c o e f f i c i e n t s SA + 2 N a r e the t r a n s f o r m a t i o n m a t r i x e l e m e n t s
c a l c u l a t e d f r o m f o r m u l a (61) in p e r t u r b a t i o n c a l c u l a t i o n .
TABLE I. LINE STRENGTHS F O R HUND'S CASE (a) IN G E N E R A L F O R M
Branches Line strengths Branches Line strengths
дл = о 2S+1 2S+1 2S+1 2S+1

ДА = + 1 ДА = - 1
f -Si 2 0 - П - 1 ) (J-B)
P(J) P(J) R(J-l)
J 2J
ň 2 ( 2 j + l) (J+0 + 1) (J-£i) (2 J +1)
00) Offl Q(J)
JO + i ) 2 J (J +1)
a+ l f - d (J +П + 1) (J +Si + 2)
R(J) R(J) P(J+1)
J+1 2 (J +1)
410 KOVÁ CS
F o r the z - c o m p o n e n t of t h e e l e c t r i c dipole m o m e n t (121) y i e l d s
,N'N"
R' Ф*. M Z ^ N „ d r (122)
F i n a l l y , an e x p r e s s i o n of the s a m e f o r m as b e f o r e i s o b t a i n e d f o r the
i n t e n s i t y , with t h e only d i f f e r e n c e that S r r h a s b e e n r e p l a c e d by
+s +J
-Л' J"
VN"
I
£=-S
Z
M=-J
J
Г, A' +E, M
r , л"+г, м
1
ЗЛ-+Е,
" N" (123)
w h e r e , in t h e s u m m a t i o n , J = J ' f o r e m i s s i o n and J = j " f o r a b s o r p t i o n , a s

b e f o r e . If in E q . (123) the t r a n s f o r m a t i o n e l e m e n t s a r e w r i t t e n in t h e i r
c a s e (b) f o r m s , a new s e l e c t i o n r u l e e m e r g e s : AN = 0, ± 1.
T h e c a l c u l a t i o n of the line s t r e n g t h s f o r t r a n s i t i o n s b e t w e e n t e r m s of
any kind and m u l t i p l i c i t y i s v e r y c u m b e r s o m e and lengthy, but v e r y
i m p o r t a n t w o r k not only f o r p h y s i c i s t s but a l s o f o r a s t r o n o m e r s . T h e
c o l l e c t e d explicit e x p r e s s i o n s f o r d i f f e r e n t t y p e s of t r a n s i t i o n s of the s a m e
m u l t i p l i c i t y up to and including s e p t e t t e r m s , and f o r t h o s e of d i f f e r e n t
m u l t i p l i c i t y up to q u a r t e t t e r m s can be found in R e f . [ 5] .
REFERENCES
[1] BETHE, H. A. , SALPETER, E. E. , Quantum Mechanics of One- and Two-Electron Atoms, Academic
Press, New York (1957).
[2] CONDON, E . U . , SHORTLEY, G. H. , The Theory of Atomic Spectra, Cambridge Univ. Press,
New York (1957).
[3] GOLDMAN. I . I . , KRIVCHENKO, V.D. , Problems in Quantum Mechanics, Pergamon Press, London,
and Addison-Wesley Publishing Co. , Reading. Mass. (1961).
[4] HERZBERG, G. , Molecular Spectra and Molecular Structure, Vol. I Spectra of Diatomic Molecules,
D. van Nostrand, New York (1950), 2nd edition.
[5] KOVÁCS, I . , Rotational Structure in the Spectra of Diatomic Molecules, Akadémiai Kiadô, Budapest,
and Adam Hilger Ltd., London (1969) or Elsevier Publishing Co. , New York (1969).
[6] KRAMERS, H . A . , Quantum Mechanics, North-Holland Publishing Co. , Amsterdam, and Interscience
Publishers, New York (1957).
[7] KRONIG, R.L. , Band Spectra and Molecular Structure, Cambridge Univ. Press, New York (1930).
The reader is referred to Refs [4] and [ 5 ] for individual papers.

IAEA-SMR-12/11
P E R T U R B A T I O N S IN T H E S P E C T R A
O F DIATOMIC M O L E C U L E S
Hélène LEFEBVRE-BRION
Centre de mécanique ondulatoire appliquée,
Paris, France
and
Laboratoire de photophysique moléculaire,
Faculté des sciences,
Orsay, France
Abstract
PERTURBATIONS IN THE SPECTRA OF DIATOMIC MOLECULES.

1. Definition of the perturbations. 2. Electronic homogeneous perturbations. 3. Spin homogeneous
perturbations. 4 . Heterogeneous perturbations. 5. Predissociations. 6. Preionizations.
1. DEFINITION O F T H E PERTURBATIONS
S o m e t i m e s , in t h e e l e c t r o n i c s p e c t r u m of a m o l e c u l e , t h e o b s e r v e d
l i n e s in a band of a s y s t e m d e v i a t e f r o m a r e g u l a r p a t t e r n . If t h e t e r m
v a l u e s of e a c h l e v e l of t h e t r a n s i t i o n a r e o b t a i n e d , t h e s e d e v i a t i o n s a r e
r e f l e c t e d in t h e r o t a t i o n a l l e v e l s of o n e s t a t e : t h i s s t a t e i s s a i d t o be
p e r t u r b e d . If a w h o l e s e t of v i b r a t i o n a l l e v e l s i s p e r t u r b e d , t h e AG c u r v e ,
w h e r e AG = T ( v + l ) - T ( v ) , c a n l o s e i t s s m o o t h c h a r a c t e r .
T h e s e d e v i a t i o n s a r e o f t e n i n t e r p r e t e d in t e r m s of a p e r t u r b a t i o n of a
l e v e l of an e l e c t r o n i c s t a t e by a l e v e l of a n o t h e r e l e c t r o n i c s t a t e w h i c h
c o m e s v e r y c l o s e t o t h e f o r m e r in a s m a l l e n e r g y r a n g e [1]. A s f o r any
p e r t u r b a t i o n p r o b l e m , it is n e c e s s a r y to find t h e b e s t s e p a r a t i o n of t h e
H a m i l t o n i a n into t w o p a r t s , t h e z e r o - o r d e r H a m i l t o n i a n g i v i n g t h e
" d e p e r t u r b e d " l e v e l s . It i s g e n e r a l l y a s s u m e d t h a t t h e s e l e v e l s b e l o n g to
two d i f f e r e n t potential c u r v e s for which the B o r n - O p p e n h e i m e r a p p r o x i m a -
t i o n would be c o r r e c t . T h u s , t h e i n t e r a c t i o n b e t w e e n t h e s e t w o s t a t e s i s
due t o t h e t e r m s n e g l e c t e d in t h e B o r n - O p p e n h e i m e r a p p r o x i m a t i o n .
T h e p u r p o s e of any p e r t u r b a t i o n study i s t o o b t a i n t h e i n t e r a c t i o n
m a t r i x e l e m e n t in o r d e r t o u n d e r s t a n d t h e o r i g i n of t h e p e r t u r b a t i o n and
in o r d e r t o o b t a i n i n f o r m a t i o n about t h e p e r t u r b i n g s t a t e . T h e c o m p a r i s o n
of t h e e x p e r i m e n t a l n u m e r i c a l v a l u e of t h i s i n t e r a c t i o n with a q u a l i t a t i v e
(or q u a n t i t a t i v e ) e v a l u a t i o n of t h i s q u a n t i t y g i v e s t h e n a r e a l u n d e r s t a n d i n g
of t h e p h e n o m e n o n . T h i s e s t i m a t i o n can be m a d e if t h e e l e c t r o n i c s t a t e s
a r e e x p r e s s e d in t e r m s of c o n f i g u r a t i o n s on m o l e c u l a r o r b i t a l s . We s h a l l
p r e s e n t e x a m p l e s t a k e n f r o m r e c e n t o b s e r v a t i o n s m a d e m a i n l y in t h e l a s t
f i v e y e a r s w h e r e both t h e p e r t u r b i n g and t h e p e r t u r b e d s t a t e s a r e known
and c r o s s .
1. 1. E x p e r i m e n t a l m e t h o d s of d e p e r t u r b a t i o n
T h e u s u a l p r o c e d u r e i s b a s e d on g r a p h i c a l m e t h o d s . If only two
r o t a t i o n a l l e v e l s i n t e r a c t w i t h e a c h o t h e r , we c a n r e p r e s e n t t h e s e two
411
412 LEFEB VRE -BRION
e n e r g y l e v e l s b e f o r e t h e p e r t u r b a t i o n by s t r a i g h t l i n e s (if c e n t r i f u g a l
d i s t o r t i o n i s n e g l e c t e d ) . T h e u n p e r t u r b e d l e v e l s , F j and F 2 , h a v i n g
d i f f e r e n t B - v a l u e s , f o r m two l i n e s of d i f f e r e n t s l o p e s w h i c h i n t e r s e c t .
T h e p e r t u r b e d l e v e l s F 1 a r e s o l u t i o n s of t h e e q u a t i o n :
Fx - F' H,
(1.1)
H,
w h e r e F i = E i + BiJ( J + 1 )
F 2 = E 2 + B 2 J ( J + 1)
the solution is:

E ' + B ' J ( J + 1)
Fx +F2 (Fi-F2)2
F' = - ± - + H12
E' +B' J ( J + 1 )
If t h e two u n p e r t u r b e d l e v e l s i n t e r s e c t at J = J c , t h e s o l u t i o n s at t h i s point a r e :
F ' ( J = JC) = F 1 ± H 1 2 = F 2 ± H 1 2
T h i s r e l a t i o n s h o w s ( s e e F i g . 1,1) t h a t at t h e c r o s s i n g point t h e d i s t a n c e
b e t w e e n t h e two p e r t u r b e d l e v e l s i s e q u a l to 2 H J 2 . T h e c u r v e s of BJ^ and
Щ a s a f u n c t i o n of J ( J + 1) a r e no l o n g e r c o n s t a n t s ( F i g . 1.2), t h e B ' - v a l u e
of t h e p e r t u r b e d l e v e l b e c o m i n g e q u a l to t h a t of t h e p e r t u r b i n g l e v e l and
v i c e v e r s a . In m a n y c a s e s , t h e c u r v e s of F ' (J) and B ' ( J ) a r e not s o
s i m p l e [2]. F o r e x a m p l e , t h i s i s t h e c a s e if a l e v e l i s " s a n d w i c h e d "
- b e t w e e n two v i b r a t i o n a l l e v e l s of the o t h e r s t a t e (Fig. 1.3). T h e B ' - c u r v e
can b e b e l l - s h a p e d : at s m a l l J , t h e p e r t u r b e d s t a t e t a k e s t h e c h a r a c t e r
of t h e l o w e r p e r t u r b i n g s t a t e and at l a r g e J it t a k e s t h e c h a r a c t e r of t h e
u p p e r p e r t u r b i n g l e v e l . In t h e e x a m p l e of F i g . 1.4, t h e p e r t u r b i n g l e v e l s
h a v e a B j - v a l u e s m a l l e r t h a n t h e B 2 ~ v a l u e of t h e p e r t u r b e d l e v e l . In p r i n -
c i p l e , t h e p e r t u r b e d l e v e l i s p e r t u r b e d by all t h e v i b r a t i o n a l l e v e l s of t h e
o t h e r e l e c t r o n i c s t a t e . In t h e c a s e of m o r e t h a n two i n t e r a c t i n g l e v e l s o r
in t h e c a s e of m u l t i p l e t s t a t e s , t h e e a s i e s t m e t h o d i s t o d i a g o n a l i z e an
i n t e r a c t i o n m a t r i x of an o r d e r equal t o t h e n u m b e r of i n t e r a c t i n g l e v e l s .
Now two c a s e s can a r i s e :
(i) H 1 2 i s i n d e p e n d e n t of J . T h e p e r t u r b a t i o n i s h o m o g e n e o u s .
(ii) H 1 2 d e p e n d s on J by a f a c t o r N/ J ( J + 1) o r (J - 1 / 2 ) . T h e p e r t u r b a t i o n i s
heterogeneous.
How it i s p o s s i b l e to d i s t i n g u i s h b e t w e e n t h e s e two t y p e s of i n t e r a c t i o n ?
In p r i n c i p l e [3], f o r J = 0, t h e h o m o g e n e o u s p e r t u r b a t i o n i s n o n - z e r o but
b e c o m e s z e r o v e r y f a r f r o m t h e c r o s s i n g point. It i s z e r o at J = 0 f o r a
h e t e r o g e n e o u s p e r t u r b a t i o n . F o r l a r g e J a n d f a r f r o m t h e c r o s s i n g point,
t h e p e r t u r b a t i o n t h e o r y g i v e s an e n e r g y s h i f t w h i c h , f o r a h e t e r o g e n e o u s
perturbation, is equal to:
_ H22 [EN/ J ( J + 1)] 2 e2

F F =
I" i F 2 - F j ~ (B 2 - В-,) J ( J + 1) " в 2 -в х
IAEA - S M R - 1 2 / 4 2 413
and b e c o m e s c o n s t a n t (see F i g . 1. 5). In p r a c t i c e , a s it i s o f t e n d i f f i c u l t

to know t h e r e a l e n e r g y o r i g i n of t h e u n p e r t u r b e d t e r m s , t h i s r u l e is not
v e r y u s e f u l f o r s m a l l J . One can s a y that t h e h o m o g e n e o u s p e r t u r b a t i o n s
extend o v e r m a n y s u c c e s s i v e l e v e l s , and o v e r t h e whole r a n g e of J . T h e
h e t e r o g e n e o u s p e r t u r b a t i o n s a r e s t r o n g in a s m a l l r a n g e of J . O t h e r
a r g u m e n t s , such a s t h e r e l a t i v e i n t e n s i t y of t h e two b a n d s , a r e u s e f u l f o r
confirmation.
FIG. 1 . 1 . Term values of one pair of perturbed levels. The term values of deperturbed levels are shown
by broken lines.
4 1 4 LEFEB VRE - B R I O N
FIG, 1 . 5 . Difference between perturbed and deperturbed term values for (a) homogeneous perturbation and
(b) heterogeneous perturbation.
T h e b e s t way to u n d e r s t a n d s e l e c t i o n r u l e s f o r t h e p e r t u r b a t i o n s i s to
give e x p l i c i t l y t h e o r i g i n of t h e i n t e r a c t i o n , i. e. t h e n a t u r e of t h e t e r m
w h i c h i s n e g l e c t e d in t h e B o r n - O p p e n h e i m e r a p p r o x i m a t i o n .
1. 2. Selection r u l e s for the perturbations
S i n c e t h e a b o v e i n t e r p r e t a t i o n s a r e given in t e r m s of v i b r a t i o n a l o r
rotational levels for the unperturbed solutions, this a s s u m e s implicitly
t h a t it i s p o s s i b l e to d e f i n e p o t e n t i a l c u r v e s , i. e. t h e w a v e f u n c t i o n s Мл
of t h e u n p e r t u r b e d s t a t e s h a v e t h e f o r m of a B o r n - O p p e n h e i m e r ( B . O . )
product.
=<Mq, R)xv, (R)e,(e,</>)

w h e r e q i s t h e w h o l e of t h e e l e c t r o n i c c o - o r d i n a t e s , R i s t h e i n t e r n u c l e a r
d i s t a n c e and 0, ф a r e t h e r o t a t i o n a l a n g u l a r c o - o r d i n a t e s , s p e c i f y i n g t h e
p o s i t i o n s of the n u c l e i in t h e l a b o r a t o r y s y s t e m .
N o t e t h a t in t h i s d e f i n i t i o n of a B.O. p r o d u c t , t h e e l e c t r o n i c w a v e f u n c t i o n $ i
i s not n e c e s s a r i l y an e x a c t s o l u t i o n t o t h e e l e c t r o n i c H a m i l t o n i a n , but
d e f i n e s a p o t e n t i a l c u r v e V\ (R) s u c h t h a t
IAEA-SMR-12/32,35 415
which will give t h e solutions xVi :
[T N + V i ( R ) ] x v . (R) = E v . x v . (R)
The i n t e r a c t i o n m a t r i x e l e m e n t HX2 is an o f f - d i a g o n a l m a t r i x e l e m e n t of
t h e t o t a l H a m i l t o n i a n H between two B.O. p r o d u c t s .
НцКф^Юх (R) e j ( e , * ) | H | < * 2 ( q , R ) Ху№) ®,(M)>
In t h e c a s e of p e r t u r b a t i o n s , t h e two i n t e r a c t i n g s t a t e s belong to t h e d i s -
c r e t e s p e c t r u m . If t h e v i b r a t i o n a l p a r t of t h e p e r t u r b i n g s t a t e Xv2 belongs
to t h e continuum of t h e nuclei, i. e. t h e p e r t u r b i n g s t a t e i s a d i s s o c i a t i v e
s t a t e , the p e r t u r b a t i o n b e c o m e s a p r e d i s s o c i a t i o n o r a p r o b l e m of i n e l a s t i c
c o l l i s i o n s . If both t h e v i b r a t i o n a l f u n c t i o n s xVl and Xv2 belong to the
continuum of the nuclei, it i s also a p r o b l e m of i n e l a s t i c c o l l i s i o n s . If t h e
e l e c t r o n i c p a r t of t h e p e r t u r b i n g s t a t e ф2 belongs to t h e continuum, it is a
p r e i o n i z a t i o n (or autoionization).
T h e e x p r e s s i o n of the t o t a l H a m i l t o n i a n is given in K l y n n i n g ' s p a p e r
(these P r o c e e d i n g s ; s e e also [4]). The n e g l e c t e d t e r m s in the n o n - r e l a t i v i s t i c
B o r n - O p p e n h e i m e r a p p r o x i m a t i o n a r e c o m p i l e d in T a b l e I.
As a n e g l e c t e d t e r m does not contain the v a r i a b l e s 0 and ф, and a s the
e f f e c t of the operator; J + d o e s not change t h e v a l u e of J , t h e m a t r i x e l e m e n t
is n o n - z e r o only if the r o t a t i o n a l f u n c t i o n s h a v e the s a m e quantum
n u m b e r J . T h e n c e the f i r s t s e l e c t i o n r u l e A J = 0 i s valid f o r all t y p e s of
perturbations.
Following the c l a s s i f i c a t i o n given by Hougen [Id], we d e f i n e the
p e r t u r b a t i o n s with r e s p e c t to t h e П quantum n u m b e r . The s e l e c t i o n r u l e
AQ = 0 gives h o m o g e n e o u s p e r t u r b a t i o n s , i. e. t h e i n t e r a c t i o n m a t r i x
e l e m e n t does not depend on t h e r o t a t i o n a l quantum n u m b e r J .
Two c a s e s can be d i s t i n g u i s h e d :
(1) H o m o g e n e o u s p e r t u r b a t i o n s due to the e l e c t r o n i c m a t r i x e l e m e n t s
Д Л = 0, A L= 0, AS = 0
In t e r m s of i n t e r s e c t i n g o r so called " d i a b a t i c " potential c u r v e s , t h i s m a t r i x

e l e m e n t is due to t h e e l e c t r o s t a t i c i n t e r a c t i o n [5, 6] . In t e r m s of n o n -
i n t e r s e c t i n g o r a d i a b a t i c c u r v e s , t h i s m a t r i x e l e m e n t i s due to the kinetic
r a d i a l n u c l e a r o p e r a t o r [3].
(2) H o m o g e n e o u s p e r t u r b a t i o n s due to the s p i n - o r b i t o p e r a t o r
with two c a s e s А Л= Д Е = 0
with AS = 0 o r ± 1
and AA = - A I = ± 1
F o r the s p i n - s p i n i n t e r a c t i o n , t h e r e i s also t h e p o s s i b i l i t y
Д Л = ДЕ = ± 2
T h e s e l e c t i o n r u l e Afž = ± 1 gives h e t e r o g e n e o u s p e r t u r b a t i o n s , i. e. t h e
i n t e r a c t i o n m a t r i x e l e m e n t depends on the r o t a t i o n a l quantum n u m b e r J .
T A B L E I. MATRIX E L E M E N T S IN P E R T U R B A T I O N CALCULATIONS
Selection rules
Neglected terms in the non-relativistic Born-Oppenheimer Nature of the
AJ = 0 always
approximation (case a) perturbation
АЛ ЛЕ AS AS5
-(A,S, l, a, v, I H e ; + T N | Л ,S, I, n,v2y Electrostatic

homogeneous 0 0 0 0
« H e S , i V ! + terms including derivatives with respect to R perturbations
1 or 2
Spin homogeneous For details
<(л .S.S.n.Vjl HS[A' ,S' , V ,ci- perturbations
different
see Table II
spin orbitals
Rotational electronic
<Л, S.E.ß.Vi I ô"~r77 (L+S"+L~S+) I Ai Zí l,ÍJ,v2> homogeneous ±1 +1
I I
perturbations
Heterogeneous
<A,S,S,n,v1 I - ~ j ( J + L " + r L + ) | Л ±l,l,Q ±1, v2> perturbations ±1
(C-uncoupling)
1 different
spin-orbital
Heterogeneous
<A,S(L,ň,v. " ÖT7 0+S" + J"S+ ) I Л , L ± 1, Q±l,v,>
£ perturbations il
I R' I
(s-uncoupling)
IAEA - S M R - 1 2 / 4 2 417
Table I s u m m a r i z e s the r e s u l t s .
Note t h a t two s t a t e s can i n t e r a c t , e i t h e r d i r e c t l y
H 1 2 = <Г21| H I S72>
o r t h r o u g h a t h i r d s t a t e (or s e v e r a l s t a t e s ) by a s e c o n d - o r d e r p e r t u r b a -
tion e f f e c t . T h i s i s s e e n if a Van Vleck t r a n s f o r m a t i o n is p e r f o r m e d [7].
<fliHn3 ) < о 3 н п 2 )
H
i2 - Ex+E2
In p r a c t i c e , t h e e f f e c t i v e i n t e r a c t i o n p a r a m e t e r is t h e s u m of t h e s e two
effects.
2. E L E C T R O N I C HOMOGENEOUS P E R T U R B A T I O N S
2. 1. N o n - r e l a t i v i s t i c d i a b a t i c and a d i a b a t i c f u n c t i o n s
In h o m o g e n e o u s p e r t u r b a t i o n s H 1 2 is an o f f - d i a g o n a l m a t r i x e l e m e n t
b e t w e e n two B.O. p r o d u c t s SE'i and having t h e s a m e q u a n t u m n u m b e r s A,
S, Г and Г2. C o n s e q u e n t l y , it i s a m a t r i x e l e m e n t of t h e t o t a l l y s y m m e t r i c
p a r t of t h e H a m i l t o n i a n
H„ + T N + H S
L e t u s d r o p t h e p a r t of t h e spin H a m i l t o n i a n H s which h a s a n o n - z e r o m a t r i x
e l e m e n t b e t w e e n such two s t a t e s (see T a b l e II). We s h a l l s e e l a t e r t h a t it
d o e s not act in p r i n c i p l e b e t w e e n t h e s a m e e l e c t r o n i c s t a t e s as t h e H ef and
T N o p e r a t o r s do. T N is t h e n u c l e a r k i n e t i c o p e r a t o r , e x p r e s s e d in t h e
r e f e r e n c e s y s t e m of t h e m o l e c u l e a s (in a. u. ):
J_ _df_ 2 _d_
R -Jt' 2p J ?
2|uR^ IdR dR dR 2 R dR 2MRZ
Let u s d r o p the Л r o t a t i o n a l p a r t of t h i s o p e r a t o r which g i v e s an i n t e r a c t i o n

dependent on J ( J + 1) but v e r y s m a l l c o m p a r e d to t h e r a d i a l p a r t [8]. We h a v e
н12=<ф1Ху1е, ^)|Ф2Ч®,> (2.1)
What i s t h e e f f e c t of t h e d e r i v a t i v e s on a B.O. p r o d u c t ? L e t u s
r e m e m b e r that both t h e v i b r a t i o n a l and t h e e l e c t r o n i c wave f u n c t i o n s depend
on R:
2 ^2 _d_ , _d_
dR 2 Фх = X^ ф + ф ^ Х + 2dR
— фф dR
— x
2 d
A 1
R dR R dR
T A B L E II. S E L E C T I O N R U L E S F O R S P I N - O R B I T AND S P I N - S P I N P E R T U R B A T I O N S
Common rules: AJ = 0 Дп± = Оа g — u; £+ £ - for spin orbit, Z+ E + f o r spin-spin.
Examples
States Configuration
= 0 — Д£= 0 - - same orbitals, or 1 or 2^ diff. spin orbitals — S.O. S.S.

1/2 ^1/2 OÏÏ'
= 0—ДА = ± 1 — Д£ = TI -- 1 or 2 diff. spin orbitals — S.O. S.S. ЗП.-ЗЕ+ OïïV - 027T3ÏÏ '
= т 2 • • ùt = f2• - 2 different spin orbitals — S.S.
0—Д2= 0 - same orbitals or 1 or 2 diff. spin orbitals — S.O. S.S.C 0 +- ' s !

AS ( = 1 — ДА =±1—Д£=Т1 - 1 or 2 different spin orbitals — S.O. S.S. ЗГ11Т . l r - О7Гв7Т - О^ 7ГЛЯ
0- 0
З 5
= ±2 — ДЕ = Т 2 - 2 different spin orbitals — S.S. д, - r;
= 0 — Д£= 0
= ± 1 — ДЕ = + 1 same orbitals or 1 or 2 diff. spin orbitals S.S.
= ± 2 — Д Е = + 2'
а
These rules on the А, 2, Q values apply to the states of the non-rotating molecule, i . e . before the Kronig symmetrization.
b 2 different spin-orbitals only for the spin-other-orbit and spin-spin contributions.
c
The spin-spin interaction is zero if 2= L' - 0.
IAEA -SMR-12/42 4 1 9
B e t w e e n two B.O. p r o d u c t s , we h a v e
-^<x V l ixv2 ><ф! U f e s + t á O ^ )
d d
Ф2 У (Xv Xv /•
V dR dR
T h e s e c o n d t e r m is z e r o s i n c e фi and ф2 a r e two d i f f e r e n t e l e c t r o n i c wave

f u n c t i o n s which can be t a k e n a s o r t h o g o n a l . T h u s
Hi2 = " ^ < X V l |xv2 Х Ф 1 |T N |ф а >- j <Ф1

dR 02 > <Xv dR <v„ >
+ <Ф i X v . l H e l 1*2 X», >
If t h e s e B.O. p r o d u c t s a r e e x a c t s o l u t i o n s of H e l , and we c a l l t h e s e
s o l u t i o n s t h e a d i a b a t i c f u n c t i o n s фА xA, we h a v e :
<Ф?хА H № 4 > 0
d /А d A
\
><фа1 ф 2 / 4XVi Xv. >
H
1 2 - " á < < uč, |т„ >-í<*í dR dR
(2.2)
F o l l o w i n g t h e n o n - c r o s s i n g r u l e [9] , t h e a d i a b a t i c p o t e n t i a l c u r v e s cannot
i n t e r s e c t and have t h e f o r m given in Fig. 2.1. Two o b j e c t i o n s a r i s e :
(i) T h e r e p r e s e n t a t i o n of c u r v e s with two m i n i m a is not in a g r e e m e n t with

t h e u s u a l e x p e r i m e n t a l p i c t u r e , w h e r e the u n p e r t u r b e d l e v e l s a r e o f t e n
t a k e n a s s o l u t i o n s of M o r s e p o t e n t i a l s ;
(ii) As t h e r e is an avoided c r o s s i n g , the ф f u n c t i o n s change v e r y r a p i d l y
with R and t h e m a t r i x e l e m e n t H A 2 can be l a r g e , in d i s a g r e e m e n t with t h e
p e r t u r b a t i o n m e t h o d . Indeed, t h e m a t r i x e l e m e n t is so l a r g e s i n c e t h e
difference Ef - is small.
FIG.2.1. Diabatic curves (heavy lines) and a d i a b a t i c curves (broken lines).

T h i s can be d e m o n s t r a t e d a s follows:
Since ф j is an e x a c t s o l u t i o n to the e l e c t r o n i c H a m i l t o n i a n
dH
If t h i s equation i s ÇL
d i f f e r e n t i a t_d_ , A r eAs p_d_
e d with e c t •to
A R , A d „А
dR 1 + H e l d R 0 ! E dR il ^ i f f l E i
A f t e r m u l t i p l i c a t i o n by ф2 and i n t e g r a t i o n we o b t a i n
dHel
<Фо dR dR dR Pi /
Since
H el V2 : E;'А л A
dHel
<Ф dR
<Ф£ (2.3)
dR E
f"E2
C o n s e q u e n t l y a n o t h e r t y p e of u n p e r t u r b e d s o l u t i o n s c a n be c h o s e n ,
such a s in [10, 11], by d e f i n i t i o n :
^ ) =0 (2.4)
dR
f o r all i and j, f o r each v a l u e of R.
As t h e r e l a t i o n :
<01 dR 2 *2>= dR<0i dR

ф
2>+ I < * 1 dR *i><*l dR
i/1,2
h o l d s f o r such f u n c t i o n s , H12 is r e d u c e d to
H?2 = < « |Hd I « , > (2.5)
As t h e s e f u n c t i o n s a r e not e x a c t solutions to t h e e l e c t r o n i c H a m i l t o n i a n ,
t h e i r p o t e n t i a l c u r v e s can i n t e r s e c t . Such f u n c t i o n s , h a v i n g t h e p r o p e r t y
of Eq. (2.4) a r e c a l l e d d i a b a t i c f u n c t i o n s [ 12] f r o m t h e t e r m i n o l o g y i n t r o -
duced by H e l l m a n n [13] in c o l l i s i o n p r o b l e m s w h e r e c r o s s i n g c u r v e s a r e
meaningful for understanding inelastic p r o c e s s e s .
In c o n c l u s i o n , if H12 i s not negligible in one o r t h e o t h e r b a s i s s e t , t h i s
m e a n s t h a t t h e s o l u t i o n s of t h e total H a m i l t o n i a n cannot be r e p r e s e n t e d by
only o n e B.O. p r o d u c t but by a l i n e a r c o m b i n a t i o n of at l e a s t two B.O. p r o -
d u c t s . On t h e o t h e r h a n d , when the a d i a b a t i c s o l u t i o n s a r e widely s e p a r a t e d ,
IAEA - S M R - 1 2 / 4 2 421
t h e H j 2 p a r a m e t e r i s s m a l l b e c a u s e t h e d e n o m i n a t o r in Eq. (2.3) i s l a r g e
and t h e B.O. a p p r o x i m a t i o n i s good. T h i s i s , f o r e x a m p l e , t h e c a s e f o r
t h e g r o u n d s t a t e of H 2 f o r which t h e n o n - a d i a b a t i c c o r r e c t i o n s h a v e b e e n
e s t i m a t e d to be of t h e o r d e r of 1 cm" 1 [14].
Now we a r e looking f o r s o l u t i o n s of the e l e c t r o n i c wave f u n c t i o n s . F o r
t h e a d i a b a t i c f u n c t i o n s , t h e v a r i a t i o n a l p r i n c i p l e is valid, and good a p p r o x i -
m a t e s o l u t i o n s can be o b t a i n e d as a s u p e r p o s i t i o n of c o n f i g u r a t i o n s .
F o r t h e d i a b a t i c f u n c t i o n s , t h e v a r i a t i o n a l p r i n c i p l e d o e s not apply and
no e x a c t solutions e x i s t , up to now. If exact s o l u t i o n s w e r e known, it i s
e a s y to s e e t h a t any l i n e a r c o m b i n a t i o n , independent of R, of t h e s e s o l u t i o n s
i s also a s o l u t i o n and t h e p r o b l e m is i n d e t e r m i n a t e if no o t h e r condition i s
i m p o s e d . But a p p r o x i m a t e s o l u t i o n s can be found, such a s o n e - c o n f i g u r a t i o n
f u n c t i o n s : T h e o p e r a t o r d/dR a c t s on a c o n f i g u r a t i o n , e x p r e s s e d in t h e f o r m
of a S l a t e r d e t e r m i n a n t , a s a m o n o e l e c t r o n i c o p e r a t o r . T h u s , t h e m a t r i x
e l e m e n t of d / d R i s z e r o if it i s t a k e n b e t w e e n two c o n f i g u r a t i o n s which d i f f e r
by at l e a s t two o r b i t a l s [15]. But t h e e l e c t r o s t a t i c o p e r a t o r b e i n g a
bielectronic operator ( due to t h e t e r m s —— 1 t h e e l e c t r o n i c H a m i l t o n i a n
^ i< j r U '
g i v e s a n o n - z e r o m a t r i x e l e m e n t b e t w e e n two c o n f i g u r a t i o n s which d i f f e r
by two o r b i t a l s : i a n d i f o r t h e f i r s t and фс and i//d f o r t h e s e c o n d
|не1 > = <0 a (l) фс( 1) Фъ(2) фр) > (2.6)
w h e r e 1 and 2 d e s i g n a t e t h e e l e c t r o n i c c o - o r d i n a t e s of t h e two e l e c t r o n s .
We s h a l l s e e t h a t , in m a n y c a s e s , h o m o g e n e o u s p e r t u r b a t i o n s a p p e a r
b e t w e e n s t a t e s w h o s e c o n f i g u r a t i o n s a r e v e r y d i f f e r e n t , n a m e l y the v a l e n c e
and t h e R y d b e r g s t a t e s .
In t h e following we s u m m a r i z e t h e d i s c u s s i o n :
Adiabatic functions Diabatic functions

(non-crossing potential curves) (crossing potential curves)
<Ф- |H e l |ф*> = 0 f o r a l l i / j and R < Ф ° | н е 1 и р / о = не
d d AD \ ==
Ф1> 10 <ф? dR 0 f o r all i, j and R
dR
Approximate solutions Approximate solutions

Mixing of c o n f i g u r a t i o n s = One-configuration approximation =
Configuration interaction functions H a r t r e e - F o c k f u n c t i o n s which d i f f e r
at l e a s t by two o r b i t a l s
2. 2. D e t e r m i n a t i o n of t h e d e p e r t u r b e d o r " d i a b a t i c " c u r v e s
If t h e e l e c t r o n i c i n t e r a c t i o n i s a s s u m e d to be independent of R, t h e
v a r i a b l e s can be s e p a r a t e d in t h e i n t e g r a t i o n of Eq. (2.5). By i n t e g r a t i o n
o v e r t h e e l e c t r o n i c v a r i a b l e s we o b t a i n
=H e <x°|x° > = Hesv.v. (2.7)

where
H„ D \
<Ф i |не11 ф
Sv£vj i s t h e o v e r l a p between t h e v i b r a t i o n a l f u n c t i o n s , the s q u a r e r o o t of a

F r a n c k - C o n d o n f a c t o r . In f a c t , as f o r any e l e c t r o n i c quantity, "the value of
H e d e p e n d s on R; h o w e v e r , t h i s d e p e n d e n c e is w e a k e r than that of t h e
v i b r a t i o n a l f a c t o r . Equation (2.7) holds even if t h e R - d e p e n d e n c e of H e l
i s l i n e a r a r o u n d t h e R - c e n t r o i d [16]. T h e n H g c a n be t a k e n equal to Hg
(R = R centioid) with t h e u s u a l d e f i n i t i o n :
<Xvj |jR | x v j .
R
centroid <x V i | x V j >
Note t h a t a l i n e a r v a r i a t i o n of H e i m p l i e s a d e p e n d e n c e on J ( J + 1) due to
c e n t r i f u g a l d i s t o r t i o n (see Section 3).
F o r any two c r o s s i n g c u r v e s , t h e R c e n t r o i d h a s t h e p r o p e r t y of being
n e a r l y equal to R e , t h e v a l u e of t h e c r o s s i n g point.
In o r d e r to o b t a i n t h e d e p e r t u r b e d o r " d i a b a t i c " c u r v e s , we can w r i t e
a m a t r i x i n c l u d i n g all the v i b r a t i o n a l l e v e l s of the two s t a t e s , f o r a c a s e
w h e r e t h e m o l e c u l e does not r o t a t e ( E q . ( l . l ) w h e r e J = 0):
Ei. - E ' 0 H 12
v, v2
Et. "E' H v2 Vi H;v122 v2

=0
E2-E' 0
E„ -E'
T h e o f f - d i a g o n a l e l e m e n t between two v i b r a t i o n a l l e v e l s of t h e s a m e
e l e c t r o n i c s t a t e i s z e r o b e c a u s e t h e s e l e v e l s a r e s o l u t i o n s to t h e s a m e
p o t e n t i a l c u r v e . H o w e v e r , as t h e m a t r i x is l i m i t e d in p r a c t i c e , it can be
u s e f u l to put a n o n - z e r o m a t r i x e l e m e n t b e t w e e n t h e s e v i b r a t i o n a l l e v e l s
of a s a m e s t a t e . T h e m e a n i n g of t h i s m a t r i x e l e m e n t is given by t h e
Van Vleck t r a n s f o r m a t i o n
12
H H'
H„
EÍ, + E ,
-Eî,
i. e. it c o m e s f r o m t h e c o m m o n p e r t u r b a t i o n of the two l e v e l s by t h e s a m e
v i b r a t i o n a l l e v e l v 2 of t h e o t h e r p o t e n t i a l c u r v e .
Then the diagonal e l e m e n t s have the f o r m
(Hv
pi'-pi .V ri)2
v v
i i L E} -E2
i
w h e r e Evj (for Vj = v i o r v 2 ) i s t h e l e v e l b e f o r e i t s p e r t u r b a t i o n by t h e
o t h e r l e v e l s , E 2 - not being i n c l u d e d in t h e m a t r i x .
IAEA - S M R - 1 2 / 4 2 423
T h e o f f - d i a g o n a l e l e m e n t b e t w e e n two v i b r a t i o n a l l e v e l s of d i f f e r e n t
s t a t e s r e p r e s e n t s only t h e i n t e r a c t i o n b e t w e e n t h e m
H 1V ' 2 ' = H 12
1 VZ *•"[ Yz
T h e d e p e r t u r b e d c o n s t a n t s d e p e n d on t h e a s s u m e d m o d e l f o r t h e d i a b a t i c
c u r v e s . If t h e d i a b a t i c c u r v e s a r e a s s u m e d to b e M o r s e f u n c t i o n s a n d if
12
E q . (2.7) i s u s e d f o r HViV]. , w e h a v e s e v e n p a r a m e t e r s to d e t e r m i n e in f i t t i n g
t h e r o o t s E 1 of t h e s e c u l a r e q u a t i o n t o t h e o b s e r v e d e n e r g i e s . This
c a n be a c h i e v e d by a n o n - l i n e a r l e a s t - s q u a r e s f i t t i n g [8, 17].
T h e s e t of t h e p e r t u r b e d v i b r a t i o n a l l e v e l s o f t e n s h o w s a s t r a n g e v a r i a -
t i o n of AG with v. T h i s v a r i a t i o n i s r e l a t e d to t h e v a r i a t i o n of t h e
o v e r l a p m a t r i x b e t w e e n t h e p a i r s of d e g e n e r a t e l e v e l s and i s m a x i m u m f o r
S m a x i m u m , i. e. at t h e c r o s s i n g p o i n t . S e c o n d a r y m a x i m a c a n a p p e a r
f o r h i g h e r l e v e l s . T h e i n s p e c t i o n of t h e w h o l e o v e r l a p m a t r i x g i v e s a n
i d e a of t h e i m p o r t a n c e of s e c o n d - o r d e r e f f e c t s . If o n e c u r v e i s i n s i d e t h e
o t h e r , t h e o v e r l a p v a r i a t i o n i s not so l a r g e but t h e s e c o n d - o r d e r e f f e c t s
c a n be m o r e i m p o r t a n t . We e n c o u n t e r t h e s a m e d i f f e r e n c e a s in t h e c a s e s
of p r e d i s s o c i a t i o n ( c a s e b o r c a s e c + ).
2. 3. P e r t u r b e d q u a n t i t i e s
T h e m i x i n g of t h e l e v e l s i s known, f o r t h e v a l u e J = 0, in t e r m s of
d i a b a t i c l e v e l s . F o r a two by two m a t r i x , we h a v e
= с Ó d Y d +C ó D x D
T, ,D D ,D D
thence for J small:
В !1= <NФ 11 |1H rot, |1 ф '1>' = с 2 lВv , + с 22B \, ,

(2.8)
В' = < Ф ' H Ф ' ) = с2В + с2В
2 2 rot 2 2 vl 1 v2
I n v e r s e l y , t h e s e r e l a t i o n s c a n b e u s e d to d e t e r m i n e t h e m i x i n g f r o m t h e
f i t t i n g of t h e p e r t u r b e d B - v a l u e s .
A n a l o g o u s r e l a t i o n s to E q s (2.8) h o l d f o r any d i a g o n a l p e r t u r b e d q u a n t i t y
s u c h a s t h e A^,1 = < Ý ; | H s o | ^(У (if t h e p e r t u r b e d s t a t e s a r e , f o r e x a m p l e ,
2
П states).
But f o r t h e t r a n s i t i o n m o m e n t , w e h a v e t h e r e l a t i o n
< х | м |Ф' 1 > = с 1 < Х | М | Ф 1 > + С 2 < Х | М | Ф 2 >

(2.9)
< Х | М | ф р = с 2 < Х | м | ф 1 > - с 1 < Х | м I Ф"2 У
T h e r e l a t i o n s a r e h e l p f u l in t e s t i n g t h e p e r t u r b a t i o n p r o c e d u r e [8]. It c a n
h a p p e n in s o m e c a s e s t h a t t h e i n t e n s i t y of o n e p e r t u r b e d b a n d b e c o m e s z e r o .
2.4. D e t e r m i n a t i o n of t h e a d i a b a t i c c u r v e s
F r o m a k n o w l e d g e of t h e H e i n t e r a c t i o n and t h e h y p o t h e s i s t h a t t h e
d e p e r t u r b e d e x p e r i m e n t a l c u r v e s a r e r e a l d i a b a t i c c u r v e s , i . e . r e l a t i o n (2.4)
424 LE FEB VRE-BRI ON
h o l d s , it i s p o s s i b l e to c a l c u l a t e the a d i a b a t i c c u r v e s which d i a g o n a l i z e t h e
e l e c t r o n i c H a m i l t o n i a n ( b r o k e n l i n e s in F i g . 2. 1)
«|не1|фА2> = о
Д
T h e s e n o n - c r o s s i n g p o t e n t i a l c u r v e s h a v e v i b r a t i o n a l l e v e l s s u c h a s Xvj
and Xv2 • B e t w e e n t h e s e v i b r o n i c l e v e l s t h e r e a r i s e s an i n t e r a c t i o n m a t r i x
e l e m e n t w h i c h now is due to t h e k i n e t i c o p e r a t o r
< V 2 = < < ^ | T N | < ^ >
T h i s e l e m e n t is s t r o n g l y d e p e n d e n t o n R b e c a u s e t h e vary strongly
with R; it can b e c a l c u l a t e d f r o m t h e s e r e l a t i o n s ( c a s e of a 2X 2 m a t r i x ) [18]
= d
Ф'j ij +d2j02
and
d
dR >=I dR
Note t h a t if a d e p e n d e n c e on R i s a s s u m e d f o r H e (Eq. 2.7), H i 2 can in f a c t

b e a s u m of two t e r m s ( E q . 2 . 1 ) , both of t h e m b e i n g i n d e p e n d e n t of J, and
it i s i m p o s s i b l e to s e p a r a t e t h e m f r o m t h e e x p e r i m e n t a l d a t a . D e p e r t u r b a -
t i o n i s a l w a y s p o s s i b l e (for a given a c c u r a c y ) but d i f f e r e n t s o l u t i o n s c a n be
found d e p e n d i n g on t h e c h o s e n m o d e l . N e v e r t h e l e s s , if t h e d e p e r t u r b e d
c u r v e s a r e s m o o t h c u r v e s , t h e d / d R t e r m s will be s m a l l ( s e e f o r e x a m p l e
t h e d i a g o n a l t e r m s in d 2 / d R 2 f o r the g r o u n d s t a t e of H 2 [19].
2. 5. E x a m p l e s of h o m o g e n e o u s p e r t u r b a t i o n s . Vklence and R y d b e r g s t a t e s
F r o m t h e a t o m i c o r b i t a l s of the g r o u n d s t a t e s of t h e c o n s t i t u e n t a t o m s ,
it i s p o s s i b l e t o c o n s t r u c t m o l e c u l a r o r b i t a l s f o r t h e m o l e c u l e . T h e l o w e s t
o r b i t a l s a r e the bonding o r b i t a l s , the u p p e r ones the antibonding o r b i t a l s .
T h e o r b i t a l s a r e f i l l e d in s u c c e s s i v e o r d e r to o b t a i n t h e c o n f i g u r a t i o n f o r
t h e g r o u n d s t a t e . F o r e x a m p l e , the g r o u n d s t a t e of t h e NO m o l e c u l e h a s
the configuration
( a l s 0 ) 2 ( a l s N ) 2 ( a 2 s 0 ) 2 (CT2SN)2 (a2p) 2 (тг2р)4 (ТГ*2р)
T h e s y m b o l 7r* m e a n s t h a t t h e ж* o r b i t a l i s a n t i b o n d i n g .
E x c i t e d s t a t e s c a n be found by t h e e x c i t a t i o n of o n e e l e c t r o n f r o m t h e
ir bonding o r b i t a l to t h e ir* a n t i b o n d i n g o r b i t a l . T h e n t h e c o n f i g u r a t i o n i s
. . . (тг2р)3 (тг*2р)2
which g i v e s o n e 2Ф, o n e 4П and t h r e e 2П s t a t e s .

T h e s e s t a t e s h a v e a l a r g e r i n t e r n u c l e a r d i s t a n c e and a s m a l l e r h a r m o n i c
c o n s t a n t t h a n t h e g r o u n d s t a t e , which h a s m o r e bonding o r b i t a l s .
IAEA - S M R - 1 2 / 4 2 425
O t h e r e x c i t e d s t a t e s c a n a l s o b e f o r m e d by an e x c i t a t i o n f r o m the
a bonding o r b i t a l to t h e antibonding 7r* o r b i t a l . T h e c o n f i g u r a t i o n :
. . . (cr2p) (7г2р)4 (7Г* 2p) 2
g i v e s t h e 4 £ " , 2 £ ~ , 2 £ + and 2 Д s t a t e s .
T h e s e s t a t e s a r e c a l l e d v a l e n c e - s h e l l s t a t e s . T h e y a r e l i m i t e d to
m o l e c u l e s and do not e x i s t in a t o m s .
Also in m o l e c u l e s , t h e r e e x i s t excited s t a t e s s i m i l a r to t h o s e in t h e
atoms. These s t a t e s a r e called Rydberg states. The excited electron is
t h e n in an o r b i t a l which is m o r e and m o r e d i f f u s e up to i o n i z a t i o n . T h e
f i r s t R y d b e r g o r b i t a l h a s a r a d i u s of about 3 Â. T h e R y d b e r g e l e c t r o n s e e s
t h e r e s t of t h e m o l e c u l e a s a c e n t r e of c h a r g e of about + 1 and t h e e n e r g y
l e v e l s a r e s i m i l a r to t h o s e of t h e h y d r o g e n a t o m and follow a p p r o x i m a t e l y
the Rydberg formula
ER = E ion " n *2
C o n s e q u e n t l y t h e p o t e n t i a l c u r v e s of t h e R y d b e r g s t a t e s r e s e m b l e t h a t of
t h e s t a t e of t h e ion to which t h e R y d b e r g s e r i e s is s a i d to c o n v e r g e .
T h e s u c c e s s i v e R y d b e r g o r b i t a l s of an a t o m give s u c c e s s i v e R y d b e r g
molecular orbitals
3s -» 3scr
Зр - Зрст
p-complex
Зрт
Зра
3 d -» Зр7г • d-complex etc.
3dó
etc.
In t h e NO m o l e c u l e , t h e l o w e s t 2П and 2 Д s t a t e s a r e t h e s t a t e s С 2 П
and F A with t h e c o n f i g u r a t i o n (
(ст2р)2(тг2р)4(3ртг) С 2 П
(а2р) 2 (тг2р)4 (3d6) F 2 A
T h e p o t e n t i a l c u r v e s of t h e s e s t a t e s a r e v e r y s i m i l a r to t h a t of t h e g r o u n d
s t a t e of t h e NO + ion, t h e X x E + s t a t e , having t h e c o n f i g u r a t i o n
(ст2р)2 (тг2р)4 X 1 L+
Both t h e В2П and В , 2 Д v a l e n c e - s h e l l s t a t e s d i f f e r s t r o n g l y f r o m the С 2 П

and F 2 A R y d b e r g s t a t e s and t h e i r M o r s e p o t e n t i a l c u r v e s can c r o s s . We
h a v e t h e following r e s u l t s f o r t h e s p e c t r o s c o p i c c o n s t a n t s :
, -1
NO Re (A) ue(cm
2
X П ground state 1.151 1904
В2П 1.418 1054

valence-shell states
В'2Д 1.302 1223
с2п 1.062 2346

Rydberg states
F2A 1.065 2372
g r o u n d s t a t e of the NO + ion 1.062 2370
T h e two c o n f i g u r a t i o n s of t h e В ' 2 Д and F 2 A d i f f e r by two o r b i t a l s .

T h e e l e c t r o s t a t i c i n t e r a c t i o n is given by t h e following e x p r e s s i o n in t h e
o n e - d e t e r m i n a n t a l a p p r o x i m a t i o n (see Eq. (2.6) [5])
H e = <а2р(1)тг2р(1) 3dó (2)тг2р(2) >

• 12
T h i s i n t e g r a l is s m a l l [5] (=450 cm" 1 ) but n o n - z e r o a s can be s e e n if t h e

o n e - c e n t r e p a r t is w r i t t e n a s t h e a t o m i c i n t e g r a l < s p |dp>.
Another e x a m p l e of such h o m o g e n e o u s p e r t u r b a t i o n s b e t w e e n v a l e n c e -
s h e l l and R y d b e r g s t a t e s a p p e a r s in t h e N 2 m o l e c u l e . T h e c o n f i g u r a t i o n of
t h e g r o u n d s t a t e is
(og2Pf („u2P)4 x1^
A f i r s t e x a m p l e a r i s e s in t h e i n t e r a c t i o n b e t w e e n t h e 1 Ец s t a t e s .
The b,:l£J v a l e n c e - s h e l l state comes mainly f r o m the configuration
(ag2pf (тги2р)3 (^g2p)
T h e f i r s t R y d b e r g s t a t e , c , : 1 £ Î , b e l o n g s to a s e r i e s which c o n v e r g e s to t h e
g r o u n d s t a t e X 2 Eg of t h e ion N 2
(ag2p)(7Tu2p)4
It h a s t h e c o n f i g u r a t i o n :
(cr g 2p) (7ru 2p) 4 (Зрстu ) ,
T h e two b lX E+ and c' s t a t e s d i f f e r by two o r b i t a l s and t h e e l e c t r o s t a t i c

i n t e r a c t i o n h a s a v a l u e of about 890 cm-i [17, 20].
A s t r o n g e r p e r t u r b a t i o n a r i s e s b e t w e e n t h e 1 П и s t a t e s of t h e N 2
m o l e c u l e : t h e c o n f i g u r a t i o n of t h e v a l e n c e - s h e l l s t a t e b-'fly is
(a 2s) (а 2р) 2 (тг 2р)4(тг 2p)

i t
T h e R y d b e r g s t a t e c 1 n u is t h e f i r s t of a R y d b e r g s e r i e s which c o n v e r g e s
to t h e ground s t a t e X 2 E g of t h e ion and h a s t h e c o n f i g u r a t i o n
IAEA - S M R - 1 2 / 4 2 427
(a u 2s) 2 (o- 2p)(7r u 2p) 4 (3p7T u )

t t
T h e R y d b e r g s t a t e о'Пц i s t h e f i r s t of a s e r i e s which c o n v e r g e s to t h e f i r s t
e x c i t e d s t a t e A 2 n u of t h e ion. T h e s t a t e о 1 ! ^ h a s t h e c o n f i g u r a t i o n
2 2 3
(а и 2 3 ) (аг2р) (7г и 2р) ( З з а ,6)
6 t t
T h e s e s t a t e s d i f f e r two by two by two o r b i t a l s (as i n d i c a t e d by a r r o w s ) .

E x p e r i m e n t a l l y , due to t h e s e two R y d b e r g s t a t e s , s t r o n g p e r t u r b a t i o n s
a p p e a r in t h e AG c u r v e of t h e b 1 !^ s t a t e . Such an i n t e r a c t i o n can be solved
only by n u m e r i c a l t e c h n i q u e s u s i n g a c o m p u t e r . F r o m a f i t t i n g to e x p e r i -
m e n t a l d a t a (the B v and E v v a l u e s ) , a d e p e r t u r b a t i o n p r o c e d u r e h a s been
p e r f o r m e d by D r e s s i e r and L e o n i [20, 8]. T h e e l e c t r o n i c i n t e r a c t i o n
p a r a m e t e r Н 0 ь h a s a m a x i m u m v a l u e of about 1500 cm" 1 and v a r i e s s m o o t h l y
with R (Fig. 2.2). If t h e d e p e r t u r b e d c u r v e s a r e a s s u m e d to be t h e t r u e
0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
RIÂ)
FIG.2.2. C a l c u l a t e d d i a b a t i c ( № ) a n d a d i a b a t i c (V J ) p o t e n t i a l c u r v e s of t h e 4I U s t a t e s of t h e N 2 m o l e c u l e
a n d v a r i a t i o n w i t h R of t h e e l e c t r o n i c d i a b a t i c i n t e r a c t i o n p a r a m e t e r s CU^j S H ß ) ( f r o m Ref. [ 8 ] ) .
R (Â)
FIG. 2 . 3 . V a r i a t i o n w i t h R of t h e a d i a b a t i c i n t e r a c t i o n m a t r i x e l e m e n t G 31 (R) ( f r o m R e f . [ 8 ] ) .
d i a b a t i c c u r v e s , i. e. if t h e i n t e r a c t i o n p a r a m e t e r h a s only an e l e c t r o s t a t i c
o r i g i n , t h e a d i a b a t i c c u r v e s can be o b t a i n e d . T h e m a t r i x e l e m e n t s
Gy (R) = - (ft 2 /2ц) I d2/dR2 > have b e e n c a l c u l a t e d by L e o n i ; e. g. the
e l e m e n t G 3 1 ( R ) , a s s o c i a t e d with t h e a d i a b a t i c p o t e n t i a l s V 3 and V 1 of P i g . 2.2
i s shown in F i g . 2.3: it v a r i e s d r a s t i c a l l y with R and i t s m a x i m u m value
i s about 7000 cm" , m u c h l a r g e r than t h e e l e c t r o s t a t i c p a r a m e t e r . T h i s
s h o w s t h a t in t h i s c a s e t h e d i a b a t i c b a s i s i n v o l v e s a s m a l l e r p e r t u r b a t i o n
t h a n t h e a d i a b a t i c one.
S o m e kind of e x p e r i m e n t a l proof of t h e v a l i d i t y of t h i s d e p e r t u r b a t i o n
h a s b e e n found. In t h e s p e c t r u m of d i a t o m i c m o l e c u l e s t r a p p e d in a r a r e -
g a s m a t r i x , it is w e l l known (but not well u n d e r s t o o d ) t h a t t h e R y d b e r g
s t a t e s d i s a p p e a r . C o n s e q u e n t l y the v a l e n c e - s h e l l s t a t e s a p p e a r in t h e
m a t r i x without any p e r t u r b a t i o n . It is, in f a c t , t h e u n p e r t u r b e d s t a t e s
which a r e o b s e r v e d , e x c e p t f o r a s m a l l e n e r g y s h i f t of t h e whole p o t e n t i a l
c u r v e by t h e m a t r i x . Such an e x p e r i m e n t h a s b e e n p e r f o r m e d in p u r e
solid N 2 [21a] and f o r N 2 t r a p p e d in m a t r i c e s [21b]. The o b s e r v e d AG
c u r v e of t h e b 1 n u s t a t e is now r a t h e r s m o o t h and h a s t h e s a m e c u r i o u s s h a p e
a s t h e d e p e r t u r b e d c u r v e (Fig. 2.4).
A n o t h e r e x a m p l e of t h e u s e f u l n e s s of t h i s d e p e r t u r b a t i o n h a s b e e n given
r e c e n t l y in t h e study of t h e e n e r g y l o s s s p e c t r u m of t h e N 2 m o l e c u l e [22]
at v e r y low e n e r g i e s . T h e r a t i o of t h e e l e c t r o n i m p a c t c r o s s - s e c t i o n s of t h e
b 1 n u and c ^ u " d e p e r t u r b e d " s t a t e s is d i f f e r e n t f r o m t h e r a t i o of t h e i r
t r a n s i t i o n m o m e n t s in t h e o p t i c a l s p e c t r u m but t h e m i x i n g of t h e s e two
s t a t e s i s i n d e p e n d e n t of t h e type of e x c i t a t i o n . U s i n g t h e c t of E q . (2.9)
we can c a l c u l a t e t h e i n t e n s i t i e s of t h e p e r t u r b e d s t a t e s , by a s s u m i n g a
r a t i o f o r t h e two c r o s s - s e c t i o n s . C o m p a r i s o n with e x p e r i m e n t h a s h e l p e d
to d i s c o v e r t h a t unknown s t a t e s h a v e b e e n e x c i t e d by e l e c t r o n i m p a c t .
IAEA - S M R - 1 2 / 4 2 429
900
ь п„
800
о
700
о<
600
500
10
FIG.2.4. C o m p a r i s o n b e t w e e n t h e v i b r a t i o n a l s p a c i n g s AG of t h e ЬЩ и s t a t e d e d u c e d f r o m m e a s u r e m e n t s
i n p u r e solid N 2 ( o ) , in N 2 t r a p p e d in a N e m a t r i x ( x ) , and t h e c a l c u l a t e d d e p e r t u r b e d v a l u e s (+) ( f r o m
Refs [ 8 , 2 1 b ] ) .
F o r h e a v i e r m o l e c u l e s , t h e d i f f e r e n c e b e t w e e n R y d b e r g and v a l e n c e -
s h e l l s t a t e s d i m i n i s h e s and c o n s e q u e n t l y , a s one c u r v e is i n s i d e t h e o t h e r ,
t h e s e c o n d - o r d e r e f f e c t s can b e c o m e i m p o r t a n t ; f o r r e c e n t e x a m p l e s
s e e [23] (PO) and [24] ( A s 2 ) .
In t h e p r e v i o u s e x a m p l e s , t h e c o n f i g u r a t i o n s of t h e e l e c t r o n i c p e r t u r b e d
s t a t e s d i f f e r by two spin o r b i t a l s and c o n s e q u e n t l y t h e i r p o t e n t i a l c u r v e s
a r e v e r y d i f f e r e n t and i n t e r s e c t . T h e r e e x i s t a l s o h o m o g e n e o u s p e r t u r b a -
t i o n s b e t w e e n s t a t e s which d i f f e r by only o n e o r b i t a l . T h e d i f f e r e n c e
b e t w e e n t h e p o t e n t i a l c u r v e s of t h e s e s t a t e s i s not so l a r g e so t h a t they
can be n o n - c r o s s i n g c u r v e s . An e x a m p l e i s given by the p e r t u r b a t i o n s
o b s e r v e d b e t w e e n R y d b e r g s t a t e s of t h e H2 m o l e c u l e c o n v e r g i n g to t h e
s a m e g r o u n d s t a t e of H 2 but to d i f f e r e n t v i b r a t i o n a l l e v e l s of t h i s s t a t e .
As t h e d e n s i t y of e l e c t r o n i c l e v e l s i n c r e a s e s n e a r t h e i o n i z a t i o n l i m i t , t h e
l e v e l v= 1 of t h e 1 n u R y d b e r g s t a t e with n= 11 i s n e a r l y d e g e n e r a t e with t h e
l e v e l v' = 2 of t h e 4 l u R y d b e r g s t a t e with n = 6 (Fig. 2.5). T h e i n t e r a c t i o n
p a r a m e t e r is v e r y s m a l l h e r e , H = 5.5 c m " 1 . In t h e c a s e of R y d b e r g s t a t e s ,
a d i a b a t i c f u n c t i o n s a r e w e l l a p p r o x i m a t e d by o n e s i n g l e c o n f i g u r a t i o n . As t h e
c o n f i g u r a t i o n s of t h e two i n t e r a c t i n g s t a t e s d i f f e r by o n e o r b i t a l , n a m e l y
the Rydberg orbital, the electronic matrix element has approximately
the f o r m :
< n í P * ^ П*рТГ>
and is n o n - z e r o , a s n* v a r i e s with R. It i s m u l t i p l i e d by t h e v i b r a t i o n a l
factor
dR
In t h e h a r m o n i c a p p r o x i m a t i o n , t h i s v i b r a t i o n a l p a r t i s z e r o e x c e p t f o r
Av = 1 f o r which it i s p r o p o r t i o n a l to \/v+ 1. T h i s r u l e h a s b e e n p r e d i c t e d
by B e r r y [25] and it i s only a p p r o x i m a t e l y v e r i f i e d s i n c e t h e p o t e n t i a l is •
anharmonic.
T h e e x p e r i m e n t a l data h a v e been i n t e r p r e t e d by H e r z b e r g and Jungen [26]
u s i n g a s o m e w h a t d i f f e r e n t a p p r o a c h , not b a s e d on t h e a d i a b a t i c f u n c t i o n s
but on a p p r o x i m a t e f u n c t i o n s w h e r e t h e R y d b e r g o r b i t a l s a r e o b t a i n e d in
t h e field of t h e f r o z e n Щ c o r e .
In all c a s e s it would b e i n t e r e s t i n g to c o m p a r e t h e d e p e r t u r b e d v a l u e s
of t h e e l e c t r o n i c i n t e r a c t i o n p a r a m e t e r to n o n - e m p i r i c a l c a l c u l a t e d v a l u e s .
E v e n if a s i n g l e - c o n f i g u r a t i o n a p p r o x i m a t i o n is u s e d , t h e c a l c u l a t i o n is
v e r y d i f f i c u l t s i n c e t h e b i e l e c t r o n i c i n t e g r a l s in Eq. (2.6) a r e r a t h e r c u m b e r -
s o m e to o b t a i n in a t w o - c e n t r e p r o b l e m and t h e c o m p a r i s o n h a s only b e e n
m a d e in two c a s e s [5, 17]. It i s a l w a y s p o s s i b l e to s a y that if a R y d b e r g
o r b i t a l of q u a n t u m n u m b e r n i s involved in t h e i n t e r a c t i o n , t h e e l e c t r o n i c
p a r a m e t e r will be p r o p o r t i o n a l to t h e n o r m a l i z a t i o n f a c t o r of t h i s o r b i t a l , i.e.
1
H„ oc 3/2
C o n s e q u e n t l y , f o r an i n t e r a c t i o n b e t w e e n a v a l e n c e s t a t e and s u c c e s s i v e
R y d b e r g s t a t e s of one s e r i e s , t h e e l e c t r o n i c i n t e r a c t i o n d e c r e a s e s with t h e
IAEA - S M R - 1 2 / 4 2 431
h i g h e r m e m b e r s of t h e s e r i e s . It is also p o s s i b l e to p r e d i c t t h a t t h e
e l e c t r o s t a t i c i n t e r a c t i o n (or t h e k i n e t i c effect) d e c r e a s e s with the m a s s
of t h e m o l e c u l e . The e f f e c t of t h e e l e c t r o s t a t i c i n t e r a c t i o n i s r e p l a c e d
by t h e e f f e c t of t h e s p i n - o r b i t i n t e r a c t i o n which i n c r e a s e s with the weight
of t h e m o l e c u l e ( s e e Section 3).
3. SPIN HOMOGENEOUS P E R T U R B A T I O N S
3. 1. Spin p a r t of t h e H a m i l t o n i a n
In t h e H a m i l t o n i a n we o m i t t e d t h e p a r t d e p e n d i n g on t h e spin c o - o r d i n a t e s .
In t h e m o s t u s u a l f o r m , t h i s t e r m i s i n t r o d u c e d with t h e h e l p of a f i r s t -
o r d e r p e r t u r b a t i o n t h e o r y , t h e r e a f t e r the (A, S, £) B o r n - O p p e n h e i m e r
f u n c t i o n s a r e o b t a i n e d and t r e a t e d in the u s u a l w a y . The spin p a r t of the
H a m i l t o n i a n c o n s i s t s of t h r e e t y p e s of i n t e r a c t i o n : e l e c t r o n s p i n - o r b i t ,
e l e c t r o n s p i n - s p i n and e l e c t r o n s p i n - r o t a t i o n . We d r o p h e r e the h y p e r f i n e
i n t e r a c t i o n s which c o m e f r o m t h e n u c l e a r spin. T h e e l e c t r o n spin r o t a t i o n
H S R = E RYjSj gives a v e r y s m a l l d i r e c t c o n t r i b u t i o n . It h a s b e e n c a l c u l a t e d
to be about 5 MHz [27] f o r t h e g r o u n d s t a t e of t h e 0 2 m o l e c u l e . It d e c r e a s e s
with t h e m a s s of t h e m o l e c u l e . T h e e x p e r i m e n t a l v a l u e s c o m e f r o m s e c o n d -
o r d e r e f f e c t s due to a c r o s s t e r m b e t w e e n H R and H s o . T h e s p i n - s p i n o p e r a t o r
h a s t h e s a m e f o r m as in a t o m s ( s e e F e n e u i l l e , t h e s e P r o c e e d i n g s ) . T h e
d i r e c t s p i n - s p i n i n t e r a c t i o n gives a v e r y s m a l l c o n t r i b u t i o n and d e c r e a s e s
with i n c r e a s i n g m a s s : it is about 1 cm" 1 f o r t h e g r o u n d s t a t e of t h e 0 2
m o l e c u l e [28] and t h e m a i n e f f e c t c o m e s f r o m t h e s e c o n d - o r d e r e f f e c t s due
to q u a d r a t i c s p i n - o r b i t t e r m s . This h a s b e e n d e m o n s t r a t e d in a g e n e r a l
way [29, 30]. T h e s p i n - o r b i t i n t e r a c t i o n , h o w e v e r , i n c r e a s e s v e r y r a p i d l y
with t h e n u c l e a r c h a r g e .
T h e e f f e c t s of f i r s t - o r d e r and s e c o n d - o r d e r p e r t u r b a t i o n t h e o r y can
be e x p r e s s e d in t h e f o r m of an e f f e c t i v e H a m i l t o n i a n [29] f o r s p i n - o r b i t
interaction
<A, S, E, П I H s o | Л , S, E, n > = АЛЕ (3.1)
and f o r s p i n - s p i n i n t e r a c t i o n
< A , S , E , ^ | H s s | A , S , E , n > = | х л { З Е 2 - S(S + 1)> (3.2)
If A (or X) is independent of R, t h e p o t e n t i a l c u r v e s of e a c h m u l t i p l e t s t a t e
do not d i f f e r f r o m the m e a n c u r v e . But, like any e l e c t r o n i c quantity,
A (or X ) d e p e n d s on R, and t h e p o t e n t i a l c u r v e s of t h e m u l t i p l e t s t a t e s a r e
not s t r i c t l y p a r a l l e l . C o n s e q u e n t l y , if t h i s d e p e n d e n c e is l a r g e , they can
be c o n s i d e r e d a s h a v i n g d i f f e r e n t s p e c t r o s c o p i c c o n s t a n t s .
3.2. Selection r u l e s
T h e g e n e r a l s e l e c t i o n r u l e f o r t h e s e two s p i n i n t e r a c t i o n s i s
ДГ2 = 0
T h e s e l e c t i o n r u l e s can be u n d e r s t o o d if t h e spin H a m i l t o n i a n is w r i t t e n in
t e r m s of t e n s o r i a l o p e r a t o r s and if the W i g n e r - E c k a r t t h e o r e m [31] is
applied in t h e following f o r m [32]:
< S ' . E . | T ( q w CS)IS. E > - ( - I ) K + Q + S ' + E ' ( S E ' , _kq _ S £ ) < s - | | T ( W (S)||S>
where ( Д is a 3 j - c o e f f i c i e n t and <S' ||т ( к ) (S) |j S> i s a r e d u c e d
m a t r i x e l e m e n t , i. e. a quantity which d e p e n d s n e i t h e r on E 1 , E n o r on the

q - c o m p o n e n t of t h e o p e r a t o r T ^ (S) of r a n k k.
T h e s p i n - o r b i t o p e r a t o r i s a s c a l a r p r o d u c t of v e c t o r i a l o p e r a t o r s
(k = 1); t h e s p i n - s p i n o p e r a t o r is a s c a l a r p r o d u c t of o p e r a t o r s of r a n k 2 (k = 2).
The p r o p e r t i e s of the 3 j - c o e f f i c i e n t s give t h e s e l e c t i o n r u l e , i. e.
(i) t h e t r i a n g u l a r r e l a t i o n g i v e s :
f o r t h e s p i n - o r b i t o p e r a t o r S' S S± 1
f o r t h e s p i n - s p i n o p e r a t o r S1 š S ± 2
(ii) t h e 3 j - c o e f f i c i e n t is n o n - z e r o only if E1 - q - E= 0
T h e s e r u l e s h e l p in obtaining s o m e r e l a t i o n between the m a t r i x e l e m e n t s of
d i f f e r e n t c o m p o n e n t s of m u l t i p l e t s t a t e s .
For example:
3. 11
2 23.
i
< 4 n 3/21 H s o y - \ - /3. i
3/2 / ~ \ 2 , 2 H,SO <4N||HS0||4I>
i _ -L
.7. 1 2
because
Z' = П - A ' = 3 / 2 - 1 = 1/2
and
Z = Q -A =3/2
// А
2 Ii 2
<4N1/2|HSO | 4 E I / 2 > = < | , 4 | H S O ^ j <4П||Н50||4Е>
We have t h e n
< 4 n 3/2l H SO 1 4 g 3 / 2 У _ J s
<4n3/2|Hso |4E1/2> 2
Note t h a t in t h e s e e x p r e s s i o n s we used t h e value of ft t o g e t h e r with its sign.

The m a t r i x e l e m e n t s between s t a t e s of c o r r e c t s y m m e t r y of K r o n i g a r e
the s a m e except f o r t h e E j s t a t e s which h a v e only one value f o r П .
IAEA - S M R - 1 2 / 4 2 433
C o n s e q u e n t l y t h e m a t r i x e l e m e n t s of t h e s e s t a t e s m u s t be m u l t i p l i e d by -J 2.
T h e b e h a v i o u r of t h e s p i n - o r b i t o p e r a t o r u n d e r t h e s y m m e t r y o p e r a t o r s
g i v e s t h e a d d i t i o n a l s e l e c t i o n r u l e s [27]
E+ — E-
g 4- u
T h e m i c r o s c o p i c s p i n - o r b i t o p e r a t o r h a s t h e f o r m [33]
( Ък ZB \ e2 1
rij x Pi(si + 2sj)
5
i i? ]
It i s t h e s u m of a m o n o e l e c t r o n i c o p e r a t o r p l u s a b i e l e c t r o n i c o p e r a t o r
( s p i n - o t h e r - o r b i t c o n t r i b u t i o n ) . E x c e p t f o r t h e c o n t r i b u t i o n of s p i n - o t h e r -
o r b i t i n t e r a c t i o n b e t w e e n u n p a i r e d e l e c t r o n s [34], t h i s H a m i l t o n i a n h a s
the form
H
so=X I {^ía^ÍK-SÍK} (3.3)
К i
where
a2 Z
eff.K
4 - 2 r3
C o n s e q u e n t l y in t h e m o l e c u l a r - o r b i t a l d e s c r i p t i o n , t h e s p i n - o r b i t o p e r a t o r
i s a m o n o e l e c t r o n i c o p e r a t o r and h a s a m a t r i x e l e m e n t only b e t w e e n two
c o n f i g u r a t i o n s which d i f f e r by one s p i n - o r b i t a l . But t h e s p i n - o t h e r - o r b i t
o p e r a t o r can h a v e m a t r i x - e l e m e n t s between two c o n f i g u r a t i o n s o r r a t h e r
e x a c t l y two f u n c t i o n s which d i f f e r by two s p i n - o r b i t a l s . T h i s is t h e c a s e
also for the spin-spin operator
<*2 V [ r ij < s i- Sj)~ 3(r t j • SjXrjj • Sj)]

Hss =
2 Л ~ъ
i. i ij
T a b l e II s u m m a r i z e s t h e r e s u l t s .
3. 3. R e l a t i v i s t i c d i a b a t i c and a d i a b a t i c c u r v e s
D e p e n d i n g on t h e s t r e n g t h of the s p i n - o r b i t i n t e r a c t i o n , we can c h o o s e
t h e i n t e r p r e t a t i o n of t h e p e r t u r b a t i o n in t e r m s of d i a b a t i c c u r v e s o r
a d i a b a t i c c u r v e s , but it is then n e c e s s a r y to r e p l a c e H e l in t h e p r e c e d i n g
e x p r e s s i o n s by H e [ + H S 0 .
In t h e u s u a l c a s e , t h e d i a b a t i c c u r v e s a r e u s e d , b e c a u s e f o r s t a t e s
of d i f f e r e n t Л and L , t h e s e c u r v e s c r o s s and
Htff= <0i |H s c K>

If t h e s t a t e s do not c r o s s , t h e s e c o n d - o r d e r e f f e c t s due to t h e p e r t u r b i n g
e l e c t r o n i c s t a t e a r e c o n t a i n e d in t h e d i a g o n a l e f f e c t i v e c o n s t a n t s and
c o n s e q u e n t l y t h e i n t e r v a l s p l i t t i n g of a m u l t i p l e t i s not c o n s t a n t a n d d e p e n d s
o n Q and v.
If t h e s p i n - o r b i t i n t e r a c t i o n i s v e r y s t r o n g , w e c a n c a l c u l a t e t h e
r e l a t i v i s t i c B o r n - O p p e n h e i m e r c u r v e and t h e c u r v e s a r e r e l a t i v i s t i c
a d i a b a t i c c u r v e s : we h a v e c a s e _c and o n l y t h e q u a n t u m n u m b e r is
d e f i n e d . T h e c u r v e s do not c r o s s and t h e i n t e r a c t i o n b e t w e e n t h e m c a n be
g i v e n by t h e k i n e t i c e n e r g y due to m i x i n g of d i f f e r e n t A, E s t a t e s .
3.4. S e m i - e m p i r i c a l e v a l u a t i o n of t h e s p i n - o r b i t m a t r i x e l e m e n t s
U s i n g e x p r e s s i o n (3.3) f o r t h e s p i n - o r b i t o p e r a t o r and a s i n g l e c o n -
f i g u r a t i o n r e p r e s e n t a t i o n * f o r t h e e l e c t r o n i c s t a t e s , it i s p o s s i b l e to e x p r e s s
t h e m a t r i x e l e m e n t s in t e r m s of m o l e c u l a r s p i n - o r b i t p a r a m e t e r s [35].
It i s e a s y to s e e t h a t t h e e f f e c t of c l o s e d s h e l l s i s i d e n t i c a l l y z e r o ; t h e o p e n
s h e l l s g i v e a n o n - z e r o c o n t r i b u t i o n and H S o can be r e d u c e d to a s u m o v e r
o n l y t h e o p e n s h e l l s . We h a v e
i • s = jřzsz ( / s" +f s+ )
Hence r e s u l t s the effective f o r m for the H s o o p e r a t o r which is often used
Hso =A L"S= A[LzSz+i(L+S"+L'S+)]
3. 5. Diagonal elements
L e t u s c o n s i d e r an e x a m p l e of а 2П s t a t e h a v i n g a (it) c o n f i g u r a t i o n : t h e
c o m p o n e n t Г2 = + 3 / 2 (A = + 1, E = + 1/2) c a n be r e p r e s e n t e d by t h e s p i n o r b i t a l
7Г a . F r o m E q . (3.1) we o b t a i n
< 1 , 1 / 2 , 1 / 2 , 3 / 2 | H S 0 I 1, 1 / 2 , 1 / 2 , 3 / 2 > = A / 2
F r o m E q . (3.3)
< 2 П 3 / 2 , 7 г | Н 8 0 | 2 П 3 / 2 , 7 г > = <7г+0' ÇKizsz|/<*>

к
H e n c e А( 2 П, it) = a , .
A s a„ i s a p o s i t i v e p a r a m e t e r , A > 0 : t h e s t a t e i s r e g u l a r .
F o r t h e 7Г3 c o n f i g u r a t i o n , t h e 2 П 3 / 2 i s ir*a (1) ir+ß(2) ir~a(3). The contri-
b u t i o n of t h e 7T+air+ ß s u b - s h e l l to t h e s p i n - o r b i t m a t r i x e l e m e n t i s z e r o
<2n3/2' * К о I 2пз/2' 7f3

> = O " ® ! ^ Sk-^sJ' =
К
H e n c e А( 2 П, ТГ3 ) = - a„ : t h e s t a t e i s i n v e r t e d .
IAEA - S M R - 1 2 / 4 2 435
F o r а 3П s t a t e c o m i n g f r o m t h e (a)(v) c o n f i g u r a t i o n , only t h e я—electron

g i v e s a n o n - z e r o c o n t r i b u t i o n . T h e c o m p o n e n t Í2 = 2 i s aa(l)ir+a(2) or
<1, 1, 1, 2 | H S 0 I 1, 1, 1, 2> = < т + а | ^ Ç K i z s z I 7г + <*> = A
А ( 3 П, cr 7г) = •§• ал
3. 6. Off-diagonal elements
O f f - d i a g o n a l e l e m e n t s can a p p e a r
(i) b e t w e e n s t a t e s of t h e s a m e o r d i f f e r e n t m u l t i p l i c i t y belonging to
t h e s a m e c o n f i g u r a t i o n (AA = A £ = 0, but AS = 0 o r ± 1 ) : i s o ~ c o n f i g u r a t i o n a l
s p i n - o r b i t e f f e c t s , f o r e x a m p l e , t h e an c o n f i g u r a t i o n g i v e s r i s e to а 3П
s t a t e and a 1П s t a t e :
< 3 n i v | H s o | 1 n i v ' > = < l , l ) 0 , l , v | H s o I 1,0,0, l , v ' >
= <тг + (1)а(2)-^=- ( a 0 + j 3 « ) , v | £ £ SL 2i s z i | тг+ (1) <j(2) (aß-ßa),v'>

i К
= 1 < 7 Г ' I ? K U>S V V . - ( A ( 3 n ) 6 v v .

К
H e r e we adopt the following h y p o t h e s i s : t h e 3П and •1П s t a t e s h a v e t h e s a m e

p o t e n t i a l c u r v e s and t h e s a m e o r b i t a l s , and A is i n d e p e n d e n t of R o r d e p e n d s
l i n e a r l y on R.
T h e s e c o n d - o r d e r e f f e c t s of t h i s i n t e r a c t i o n give t h e m a j o r p a r t of t h e
e f f e c t i v e s p i n - s p i n p a r a m e t e r s [27, 36].
(ii) b e t w e e n s t a t e s of d i f f e r e n t A and £ v a l u e s (ДЛ = - AL = ± 1).
Let u s now c o n s i d e r t h e CO p e r t u r b a t i o n s . An e x a m p l e of such p e r -
t u r b a t i o n s known f o r a long t i m e (Ref. [ l a ] is t h e p e r t u r b a t i o n of t h e v i b r a -
t i o n a l l e v e l s of t h e а 3П and A 1 !! s t a t e s of t h e CO m o l e c u l e , which b e l o n g
to t h e (я-2р)4(сг2р)(7г*2р) e l e c t r o n i c c o n f i g u r a t i o n , by t h e a ' 3 £ + , e 3 £ " , d 3 A ,
I1^", s t a t e s which b e l o n g to t h e (7r2p)3 (ст2р)2 (ir*2p) c o n f i g u r a t i o n .
T h e s e two c o n f i g u r a t i o n s d i f f e r by one o r b i t a l and an i n t e r a c t i o n can
a p p e a r b e t w e e n the s a m e c o m p o n e n t s of t h e s e s t a t e s which d i f f e r in
the Л and S v a l u e s .
R e c e n t m o l e c u l a r - b e a m m e a s u r e m e n t s c o m b i n e d with t h e s p e c t r o s c o p i c
d a t a h a v e given a lot of i n f o r m a t i o n on t h e l e v e l s [37]. With t h e h e l p of
a d e g e n e r a t e s e c o n d - o r d e r p e r t u r b a t i o n m e t h o d to e x p r e s s t h e m a t r i x
e l e m e n t s and a n o n - l i n e a r l e a s t - s q u a r e s - f i t p r o c e d u r e , t h e e l e c t r o n i c
p e r t u r b a t i o n p a r a m e t e r s h a v e b e e n d e t e r m i n e d f o r all i n t e r a c t i n g p a i r s .
If t h e o r b i t a l s of a given c o n f i g u r a t i o n a r e a s s u m e d to be t h e s a m e f o r all
the states coming f r o m this configuration, relations between these electronic
m o l e c u l a r p a r a m e t e r s can be found; if, f o r e x a m p l e ,
1= <> fKiX (3.5)
3 n
< i'vl^ L I % - v ' > =iaSvv. (3.6)
i К
and
<1n1v ^ I3AlV'>=^ aSvv.

i К
In f a c t , t h e s i n g l e - c o n f i g u r a t i o n r e p r e s e n t a t i o n is only an a p p r o x i m a t i o n
f o r the calculation of such m a t r i x e l e m e n t s : it gives a r e l a t i v e e r r o r of up
to 40% in t h i s s p e c i a l c a s e [38]. However, it is s o m e t i m e s convenient to
u s e t h i s r e p r e s e n t a t i o n in o r d e r to get an e x p r e s s i o n of the m o l e c u l a r
p a r a m e t e r s in t e r m s of a t o m i c p a r a m e t e r s .
3. 7. Diagonal constants
If a s i m p l e development of the m o l e c u l a r o r b i t a l is known in t e r m s of

a t o m i c o r b i t a l s , the m o l e c u l a r p a r a m e t e r can be e x p r e s s e d as a s u m of
£ a t o m i c p a r a m e t e r s [39]. F o r example, the excited s t a t e B 3 n g of N2 has
t h e c o n f i g u r a t i o n (cr2p)(7r*2p).
Now we have
7Г
* 2 р " 7z (2p7rN
i "2p74 )
and
<тг*2р I Y ?к I **2P> = I < 2 Р Ч I 4 I 2 P % > + Î <2PTN2 I 4 I2P^2 >

к
w h e r e ÇN is the s p i n - o r b i t a t o m i c p a r a m e t e r .
The n e g l e c t of the other t e r m s (called t w o - c e n t r e i n t e g r a l s ) can be
j u s t i f i e d [40]. Then A(B 3 n g ) = + ^ cm_1 =
+ 3 6 сш" 1 ( e x p e r i m e n t a l value:
42. 3 cm" 1 ).
3. 8. O f f - d i a g o n a l constants
The r e l a t i o n s for the s t e p - u p and s t e p - d o w n o p e r a t o r s for a t o m i c

orbitals are
£+ ф e x = «J £ U + 1) - X(X + 1) Ф $ 1 for e x a m p l e £*pa = pír
Л'ф „ > = 71(1

+ 1) - X(X - 1) ф e for e x a m p l e £ ртг = pa
IAEA - S M R - 1 2 / 4 2 437
If t h e cr2p and 7r2p m o l e c u l a r o r b i t a l s a r e a s s u m e d to h a v e a well d e f i n e d

v a l u e f o r St t h e s e r e l a t i o n s can be extended to t h e m o l e c u l a r o r b i t a l s .
T h i s would b e a p p r o x i m a t e l y t r u e f o r h y d r i d e s . If t h e p o t e n t i a l c u r v e s
of t h e two s t a t e s a r e a s s u m e d to be i d e n t i c a l , SVV' =<5VV' . F o r e x a m p l e ,
f o r t h e 2rijy2(7r) and ^ ^ ( a ) s t a t e s :
< 4 / 2 , V | H s o I 2 £ 1 / 2 , V > = 0+ß I ÇK í V I era > S vv ,

к
T h e s e h y p o t h e s e s a r e known a s t h e p u r e - p r e c e s s i o n h y p o t h e s e s [41].
3. 9. R - d e p e n d e n c e of t h e spin i n t e r a c t i o n s
L i k e the d i a g o n a l c o n s t a n t s A, t h e o f f - d i a g o n a l c o n s t a n t a can v a r y with

If l i n e a r d e p e n d e n c e on R i s a s s u m e d
Ня
a(R) = a + {R
e S ~Rz]
T h e e l e c t r o n i c p a r a m e t e r is t h e value t a k e n at t h e R c e n t r o i d . T h e r e f o r e ,
t h e e f f e c t of t h e r o t a t i o n a l o p e r a t o r can give a t e r m depending on J ( J + 1)
I H s o (R) | f t > = a v v . + a j J ( J + l)
where
A g
a , = У <A, E,v IH » |A-, X ' , v " > < ' v"|B(R)|A'E'v'>
J /_, i so i ' ' ^ E - E
V •
v V"
+ a s i m i l a r t e r m f o r A, E, v
and we can d e r i v e f o r a j an e x p r e s s i o n s i m i l a r to A j [42]:
B2re /da Л .i.o
or
a = 2Aj a
J ~
3. 10. Forbidden transitions
In t h e m i x i n g of two n e a r l y d e g e n e r a t e s t a t e s of d i f f e r e n t m u l t i p l i c i t y ,
" e x t r a " r o t a t i o n a l l i n e s can a p p e a r . F o r e x a m p l e , if a 3 E + s t a t e which
cannot r a d i a t e to t h e singlet ground s t a t e , is mixed with а ХП s t a t e , it t a k e s

one half of the c h a r a c t e r of t h i s -"fl s t a t e in t h e c r o s s i n g r e g i o n and can
t h e n r a d i a t e to the singlet ground s t a t e .
Even if t h e i n t e r a c t i n g s t a t e s of d i f f e r e n t multiplicity a r e widely
s e p a r a t e d , and if the shift of the levels is negligible, the m i x i n g can be
s u f f i c i e n t to give r i s e to v i b r a t i o n a l f o r b i d d e n t r a n s i t i o n s , i. e. t r a n s i t i o n s
f o r b i d d e n by t h e dipole m o m e n t t r a n s i t i o n o p e r a t o r ц, such as t r a n s i t i o n s
between s t a t e s of d i f f e r e n t multiplicity. We have in t h i s c a s e
/<,
< S , nо , V
IIn le, о . v 'Л> = V
/ <S,ft,vlHso ls",ft,v")<s",n,v" MS',Q',v')
V"
w h e r e | S " , f 2 ) is the contaminating s t a t e .

A c c o r d i n g to t h i s e x p r e s s i o n , the intensity is no longer given by the
F r a n c k - C o n d o n p r i n c i p l e . Only if both the s p i n - o r b i t m a t r i x e l e m e n t and
the e l e c t r o n i c t r a n s i t i o n m o m e n t /ue; a r e a s s u m e d independent of R, and if
the d e n o m i n a t o r is taken equal to a constant AE, does the F r a n c k - C o n d o n
p r i n c i p l e s t i l l apply [43]
<S,n,v|n|S'.n'.v,>
A good e x a m p l e is given by the 3П - Х 1 £ + t r a n s i t i o n s . F o r the non-

r o t a t i n g m o l e c u l e , the mixing is allowed through the s p i n - o r b i t o p e r a t o r ,
between only t h e 3 П 1 s u b s t a t e and the 1 П 1 s t a t e coming f r o m the s a m e
configuration, but when the molecule r o t a t e s , the t h r e e s u b s t a t e s mix
and t h r e e subbands can a p p e a r , depending on the r a t i o A / B v .
As t h e m i x i n g of the 3 П 2 and 3П0 s u b s t a t e s with the 3 П 1 component
CQJ (J) depends on J , the l i f e t i m e of each component i s d i f f e r e n t and is given
by the f o r m u l a
A v v „ J C ( i i (J)
It will v a r y with J . F i g u r e 3.1 shows t h e r e s u l t for the а 3 П - X 1 E + C a m e r o n

s y s t e m of CO [44]. In h e a v i e r m o l e c u l e s such as CS [45], t h e s y s t e m has
t h e a p p e a r a n c e of a ^ - 1 E + t r a n s i t i o n .
A m o r e complex e x a m p l e of the v a r i a t i o n with J of t h e l i f e t i m e is given
by the d 3 A s t a t e of CO which is not the lowest s t a t e . T h e r e is competition
between the d i r e c t r a d i a t i v e p r o c e s s (d 3 A - а 3 П e m i s s i o n ) and the forbidden
t r a n s i t i o n of the ground s t a t e which b e c o m e s allowed due to the mixing by
s p i n - o r b i t i n t e r a c t i o n of the 3 Ai level with t h e level [46].
If t h e r e is a mixing with s t a t e s of d i f f e r e n t values of A, a n o m a l i e s in
the b r a n c h i n t e n s i t i e s can a p p e a r as a r e s u l t of the competition between
two d i f f e r e n t t r a n s i t i o n m o m e n t s [47]: one p a r a l l e l and the o t h e r p e r p e n -
d i c u l a r . An e x a m p l e is given by the f o r b i d d e n t r a n s i t i o n a4 Z~ - Х 2 П in
t h e G e F m o l e c u l e [48] or in the SnCl m o l e c u l e [49]. The s p i n - s p i n constant
of t h e 4 E " s t a t e Is due to s e c o n d - o r d e r s p i n - o r b i t e f f e c t s : the l a r g e s t c o n t r i -
bution p r o b a b l y c o m e s f r o m a mixing of the 4 E ï / 2 component with the
IAEA - S M R - 1 2 / 4 2 439
О 5 10 15 20 25
J (ROTATIONAL LEVEL)
FIG.3.1. C O ( a 3 I l ) r a d i a t i v e l i f e t i m e vs r o t a t i o n a l l e v e l ( f r o m R e f . [ 4 4 ] ) .
i s o c o n f i g u r a t i o n a l 2 Ef/2 s t a t e (атг2 c o n f i g u r a t i o n ) and with t h e X Щ/ 2

c o m p o n e n t of t h e ground s t a t e . T h e 4 £3/2 c a n only be m i x e d with t h e
X 2 П3/2 c o m p o n e n t (ЛП = 0). C o n s e q u e n t l y , t h e dipole t r a n s i t i o n m o m e n t
f o r t h e 4 £I/2 s u b s t a t e i s
<4£"1/2| Х 2 П > = a < 2 £ i / 2 I ц\ X 2 n 1 / 2 i 3/2 >+b<X2n3/2 | Х2П3/2>
= ац +Ьм..
However,
4
< E 3 / 2 I P I X2 П > = С <Х2П3/2 I Ц I X2 П3/2 > = С U I
4
T h i s could explain why t h e Ез/2-Х2П1/2 s u b s y s t e m d o e s not a p p e a r .
3. 11. Rotational electronic homogeneous perturbations
In T a b l e I, t h e f i r s t t e r m c o m i n g f r o m H r o t is
1
2 (L S + L S )«=B(L S + L S )
2pR
T h e s e l e c t i o n r u l e s a r e t h e s a m e a s f o r t h e p a r t of t h e s p i n - o r b i t o p e r a t o r
S S with A S = 0 , i . е. Д Л = ± 1 , Д Е = ? 1 , Д П = 0, but it m u s t
к i
b e n o t e d [37] t h a t t h e o p e r a t o r
i j i i<j
i s d i f f e r e n t f r o m t h e s p i n - o r b i t o p e r a t o r , cf. E q . (3.3). T h u s i n t e r a c t i o n
t e r m s c a n o c c u r b e t w e e n d e t e r m i n a n t s w h i c h d i f f e r by two s p i n o r b i t a l s .
Let us note also that i n t e g r a t i o n over the v i b r a t i o n a l p a r t does not give
a n o v e r l a p i n t e g r a l , but < v | l / 2 |uR 2 | v ' = В v v ,, w h i c h v a r i e s a s S v v . and
w h i c h i s e q u a l to В in t h e p u r e - p r e c e s s i o n r e l a t i o n .
F o r e x a m p l e , in t h e CO p e r t u r b a t i o n s we h a v e
<4, v (L+S" + L - S + ) | 3 E l v .> = bBvv. (3.7)
w h e r e b = <( 7r+| | ст)>.

E x p e r i m e n t a l l y , t h i s c o n t r i b u t i o n c a n n o t be s e p a r a t e d f r o m t h a t of t h e
s p i n - o r b i t o p e r a t o r (Eq. (3.6)) e x c e p t by i s o t o p i c e f f e c t s .
4. HETEROGENEOUS PERTURBATIONS
4. 1. The l-uncoupling operator
T h e p a r t of t h e r o t a t i o n a l o p e r a t o r w h i c h g i v e s t h e i - u n c o u p l i n g
o p e r a t o r y i e l d s t h e i n t e r a c t i o n b e t w e e n s t a t e s h a v i n g AA = ± 1 a n d AS = 0
s o t h a t AQ = ± 1. T h e s a m e e x a m p l e of t h e CO m o l e c u l e g i v e s an i n t e r a c t i o n
<Xn1>v|- - ^ r ( J + L
" +J"L+)| \ t V . >=-bB№. ^J(J+1)
t
A s J + L" = J + Z y £ [ , t h i s i s a m o n o e l e c t r o n i c o p e r a t o r . The e l e c t r o n i c p a r t
i
i s t h e s a m e a s in t h e p r e c e d i n g i n t e r a c t i o n , but o w i n g to t h e J + o p e r a t o r
it d e p e n d s o n J . T h i s t e r m g i v e s the r o t a t i o n a l c o u p l i n g in c o l l i s i o n p r o b l e m s .
In t h e u n i t e d - a t o m s a p p r o x i m a t i o n o r in t h e p u r e - p r e c e s s i o n a p p r o x i m a t i o n
we h a v e
b=V2; В ,= В
4.2. The s-uncoupling operator
Generally, this o p e r a t o r m i x e s d i f f e r e n t c o m p o n e n t s of t h e s a m e s t a t e
and d o e s not g i v e a " p e r t u r b a t i o n " . H o w e v e r , an e x a m p l e of p e r t u r b a t i o n
due to t h i s o p e r a t o r h a s b e e n r e c e n t l y o b s e r v e d in t h e g r o u n d s t a t e of t h e
NSe m o l e c u l e [50]. A s in t h i s m o l e c u l e t h e s p i n - o r b i t c o u p l i n g c o n s t a n t A
has the s a m e o r d e r of m a g n i t u d e a s t h e h a r m o n i c c o n s t a n t , a n e a r d e g e n e r a c y
IAEA - S M R - 1 2 / 4 2 441
b e t w e e n t h e v = 2 l e v e l of t h e X 2 n i / 2 s u b s t a t e and t h e v = 3 l e v e l of t h e
Х 2 П 3 /2 s u b s t a t e t a k e s p l a c e . T h e i n t e r a c t i o n b e t w e e n t h e s e two l e v e l s i s
g i v e n by
<4/2- VL-^Jp- ( j V + j V ) |2N3/2,v') =< V | - - ^ 2 |V + 1 > S / J ( J + 1)
= 2 •Jv+L J ß e / Ш е N/J(J + 1)
in t h e h a r m o n i c a p p r o x i m a t i o n .
FIG.4.1. I n t e r a c t i o n b e t w e e n r o t a t i o n a l l e v e l s of a l o w e r r e g u l a r 2П s t a t e a n d a n u p p e r Z
Z+ state.
4.3. A-doubling
If t h e e f f e c t of t h e p e r t u r b i n g s t a t e s can b e t r e a t e d by s e c o n d - o r d e r
p e r t u r b a t i o n t h e o r y , t h e e f f e c t s due to t h e SL-uncoupling o p e r a t o r , c o m b i n e d
with t h e s p i n - o r b i t o p e r a t o r , g i v e t h e A - d o u b l i n g . F o r two s t a t e s of
d i f f e r e n t A (but s a m e S), t h e s e o p e r a t o r s a c t in d i f f e r e n t w a y s on t h e
c o m p o n e n t s of d i f f e r e n t p a r i t y . T h e d i f f e r e n c e b e t w e e n t h e s e e f f e c t s l i f t s
t h e d e g e n e r a c y b e t w e e n t h e e - and f - l e v e l s ( s e e F i g . 4.1) w h e r e t h e e - l e v e l s
h a v e t h e p a r i t y (- 1) J ~ 1 / 2 and t h e f - l e v e l s h a v e t h e p a r i t y - ( - 1 ) J " 1 / 2 ( s e e [47]).
We s h a l l not give h e r e c o m p l e t e e x p r e s s i o n s of t h e i n t e r a c t i n g m a t r i x . We
want to e m p h a s i z e t h a t t h e s a m e t y p e of m a t r i x e l e m e n t s a p p e a r in i n t e r -
a c t i n g m a t r i c e s b e t w e e n d i f f e r e n t s t a t e s : f o r 2П s t a t e s , t h e s h i f t at t h e
o r i g i n of a 2 n i / 2 , v l e v e l i s given by
_V <2ПУЦА1/| 2
Е у . ) < 2 Е у . | j A L * [ 2 Пу>
2
T h e s u m i s o v e r a l l v i b r a t i o n a l l e v e l s of t h e n e i g h b o u r i n g L states. The
A - d o u b l i n g of t h e 2 s t a t e i s r o u g h l y given by
AVFE = p v (J + i )
where
<2nv|AL+|2£v.X2z:v.|BL-|2nv>
PV=7 2
• zV' E
n"v " E ,
T h e Л - d o u b l i n g of t h e ^ 3 / 2 c o m p o n e n t i s
Avef = q ( J + i ) 2
with
< 2 N V | B L + | 2 E V . > < 2 E V . |BL" | 2 N V >
E E
n - £
If o n l y o n e v i b r a t i o n a l l e v e l i s i n t e r a c t i n g with S v y = 6VV. , t h e s u m i s
r e d u c e d to t h e p r o d u c t of e l e c t r o n i c e l e m e n t s of t h e f o r m
a = < 2 П I AL + | 2 £ > and ß = < 2 n | B L + | 2 E >
1 a2 2a ß 2 g2
0 = Р = Ч =
4Е П -Е г Е п - Е 2 Еп"ЕЕ
(Note t h a t t h e K o v a c s 1 p a r a m e t e r s i n c l u d e t h e v i b r a t i o n a l o v e r l a p ; if
S v v . =5VV. , ? =a/2 and rj = ß / 2 . )
In t h i s f o r m w e c a n s e e t h a t t h e A - d o u b l i n g of t h e 2 I1I/2 s t a t e i s
r e f l e c t e d in t h e p - d o u b l i n g of t h e 2 £ I / 2 s t a t e and p = 7 [51]. If now t h e p u r e -
p r e c e s s i o n approximation is introduced we have
i A 2 l ( l +1) 2 A B I ( i + 1) 2 B 2 i ( i +1)
= q
° 4 En-E£ P" En-Ez " En-E£
T h e s e r e l a t i o n s h o l d only in t h e s i n g l e - c o n f i g u r a t i o n r e p r e s e n t a t i o n with
o n e u n p a i r e d e l e c t r o n . F o r e x a m p l e , in t h e c a s e w h e r e t h e 2 E s t a t e
c o m e s f r o m t h e итг2 c o n f i g u r a t i o n , t h e s e r e l a t i o n s m u s t b e m o d i f i e d [52].
In m a n y c a s e s t h e o n e - c o n f i g u r a t i o n a p p r o x i m a t i o n i s not s u f f i c i e n t to
e x p l a i n t h e m a g n i t u d e of t h e o b s e r v e d v a l u e s and s o m e t i m e s w r o n g r e s u l t s
a r e o b t a i n e d w h e n t h e above e x p r e s s i o n s a r e u s e d to d e t e r m i n e t h e s i g n
of A [53].
F o r 3П s t a t e s i n t e r a c t i n g with 3 £ o r 3 Д s t a t e s , s i m i l a r p a r a m e t e r s
t o t h e o, p and q p a r a m e t e r s a p p e a r . U n f o r t u n a t e l y , t h e n o t a t i o n in t h e
l i t e r a t u r e i s c o n f u s i n g . T h e f o l l o w i n g c o r r e s p o n d a n c e e x i s t s f o r 3П s t a t e s
i n t e r a c t i n g with 3 E s t a t e s :
R e f . [54] Ref.[32]
о (3E) -7/2 A0 - 4BJ + B 0
P(3£) -«' 8 B i ~ 8Bq
q(3E) -2e 4B0

IAEA - S M R - 1 2 / 4 2 443
P e r t u r b a t i o n s in Л - d o u b l i n g a r e t h e r e f l e c t i o n of p e r t u r b a t i o n s by a
v i b r a t i o n a l l e v e l which can belong to the s t a t e r e s p o n s i b l e f o r the
Л - d o u b l i n g . T h i s p e r t u r b a t i o n i s due to the s p i n - o r b i t o p e r a t o r
( p e r t u r b a t i o n of t h e v= 1 3 П s t a t e of OH + by a l e v e l of l ť s t a t e [55]), to
t h e s - u n c o u p l i n g o p e r a t o r [50,42] o r to the .<!-uncoupling o p e r a t o r ( p e r -
t u r b a t i o n of a l e v e l of t h e 2П s t a t e of CS* by a l e v e l of X 2 £ + ground s t a t e [56].
The c o n f i g u r a t i o n of t h e two e l e c t r o n i c s t a t e s m u s t d i f f e r at m o s t by
one o r b i t a l , but s o m e " a c c i d e n t a l " i n t e r a c t i o n can a p p e a r t h r o u g h a t h i r d
s t a t e (for e x a m p l e the h e t e r o g e n e o u s p e r t u r b a t i o n between t h e D 2 £ +
R y d b e r g s t a t e of NO and t h e В2П n o n - R y d b e r g s t a t e i s due to the e l e c t r o -
s t a t i c m i x i n g of t h e В 2 П with t h e С 2 П R y d b e r g s t a t e [57]).
5. PREDISSOCIATIONS
5. 1. C h a r a c t e r i z a t i o n of p r e d i s s o c i a t i o n s
If the p e r t u r b a t i o n is due to a r e p u l s i v e s t a t e p r e d i s s o c i a t i o n will
a r i s e [58]. T h e r e i s a c h a r a c t e r i s t i c f e a t u r e of p r e d i s s o c i a t i o n : the d i s c r e t e
l e v e l t a k e s t h e c h a r a c t e r of t h e continuum s t a t e and if t h e p r e d i s s o c i a t e d
l e v e l i s the f i n a l s t a t e of t h e e l e c t r o n i c t r a n s i t i o n , t h e line h a s a L o r e n t z i a n
s h a p e whose h a l f - w i d t h i s given by t h e f o r m u l a
r =27r H
v l vE | 2 P(E)
w h e r e p i s t h e l e v e l d e n s i t y in t h e continuum at the e n e r g y E.
T h i s c o r r e s p o n d s to a n o n - r a d i a t i v e l i f e t i m e (given in s e c o n d s )
r nr = Г 5 X 1 0 " 1 2' / r (cm* 1 )
C o n s e q u e n t l y a p r e d i s s o c i a t e d i n i t i a l l e v e l of a t r a n s i t i o n will e m i t only if
its non-radiative lifetime is longer than its radiative lifetime. Otherwise
t h e r e a r i s e s a m o r e o r l e s s sudden b r e a k i n g off of the l e v e l s a c c o r d i n g to
t h e s t r e n g t h of t h e p r e d i s s o c i a t i o n .
T h e i n t e r a c t i o n m a t r i x e l e m e n t HvE h a s t h e s a m e f o r m a s f o r a
p e r t u r b a t i o n and can be f a c t o r i z e d into a constant e l e c t r o n i c p a r t and a
v i b r a t i o n a l p a r t w h e r e t h e v i b r a t i o n a l function of t h e r e p u l s i v e s t a t e belongs
to t h e continuum
HÍ|= <*i l H 1*2 > < X v | x E > (5.1)

As t h e XE v i b r a t i o n a l function e x t e n d s up to infinity o r to a wall which l i e s
at s o m e l a r g e i n t e r n u c l e a r d i s t a n c e , the a m p l i t u d e of the " b o x - n o r m a l i z e d "
continuum wave f u n c t i o n i s r e d u c e d . Intuitively, f o r an e l e c t r o n i c i n t e r a c t i o n
of t h e s a m e value, the m a t r i x e l e m e n t will be s m a l l e r f o r p r e d i s s o c i a t i o n
than f o r p e r t u r b a t i o n (see P i g . 5.1).
In t h e g e n e r a l c a s e , the p r e d i s s o c i a t i n g s t a t e is unknown. Two c a s e s
of c r o s s i n g can a p p e a r :
(i) t h e i n n e r c r o s s i n g o r o n t h e l e f t side of t h e s t a b l e p o t e n t i a l c u r v e
( c a s e s b" o r с in t h e Mulliken [59] notation);
(ii) t h e o u t e r c r o s s i n g o r o n t h e r i g h t side of t h e p o t e n t i a l c u r v e ( c a s e s b +
or c+).
444 LE FEB VRE-BRI O N
T h e study of t h e l i n e width v a r i a t i o n with v and J can give s o m e i n f o r m a -

t i o n about t h e c a s e of c r o s s i n g . As in t h e c a s e of p e r t u r b a t i o n s t h e v a r i a t i o n
of t h e o v e r l a p f a c t o r with v i s l a r g e r f o r a r i g h t - s i d e c r o s s i n g [60] t h a n f o r
an i n n e r c r o s s i n g [61]. H o w e v e r , in a given v i b r a t i o n a l l e v e l t h e width
v a r i e s with J . T h e line width v a r i a t i o n with v and J follows t h e o s c i l l a t o r y
b e h a v i o u r of the o v e r l a p f a c t o r . If p r e c i s e d e t e r m i n a t i o n s of Г f o r d i f -
f e r e n t r o t a t i o n a l l e v e l s a r e a v a i l a b l e , an a n a l y t i c a l f o r m can be a s s u m e d
f o r t h e r e p u l s i v e p o t e n t i a l , t h e o v e r l a p f a c t o r s can be c a l c u l a t e d , and t h e
c r o s s i n g point and t h e s h a p e of t h e r e p u l s i v e c u r v e can b e d e d u c e d f r o m a
fit b e t w e e n e x p e r i m e n t a l and c a l c u l a t e d h a l f - w i d t h s . Using a s e m i - c l a s s i c a l
m e t h o d , a n a l y t i c a l e x p r e s s i o n s f o r the line w i d t h s a s a f u n c t i o n of v and J
h a v e b e e n given [62]. T h e n , a s t h e o v e r l a p i n t e g r a l v a l u e i s c a l c u l a t e d ,
t h e e l e c t r o n i c p a r t can be o b t a i n e d f r o m Г .
A n o t h e r p o s s i b i l i t y i s to m e a s u r e not t h e line widths but t h e l i f e t i m e s .
It i s t h e only p o s s i b i l i t y in t h e c a s e of weak p r e d i s s o c i a t i o n s w h e r e t h e
n o n - r a d i a t i v e l i f e t i m e r n r h a s t h e s a m e o r d e r of m a g n i t u d e as t h e r a d i a t i v e
l i f e t i m e т г : f o r e x a m p l e а т пг of 10"9 s g i v e s a width of about 5X10" 3 c m " 1 ,
which i s s m a l l e r t h a n t h e n a t u r a l width. Such m e a s u r e m e n t s of t h e t o t a l
l i f e t i m e r ( w h e r e т ' 1 = тг-1 + т"Пг ) f o r e a c h r o t a t i o n a l l e v e l h a s b e e n r e c e n t l y
m a d e to study p r e d i s s o c i a t i o n of t h e A 2 £ + s t a t e of OH [63].
5.2. Selection r u l e s
The r u l e s for predissociation are exactly the s a m e as for perturbation.

P r e d i s s o c i a t i o n with AS / 0 is not f o r b i d d e n s i n c e t h e s p i n - o r b i t i n t e r a c t i o n
i s t h e m o s t f r e q u e n t r e a s o n f o r a p r e d i s s o c i a t i o n . Some i n f o r m a t i o n about
t h e p r e d i s s o c i a t i n g s t a t e can b e obtained f r o m an e s t i m a t i o n of t h e e l e c t r o n i c
m a t r i x e l e m e n t . F o r e x a m p l e , t h e l e v e l v= 6 of t h e A 2 £ + s t a t e of OH i s
p r e d i s s o c i a t e d by a s t a t e which goes to t h e n o r m a l s t a t e s of t h e a t o m s .
F o l l o w i n g t h e W i g n e r - W i t m e r r u l e s , t h i s s t a t e can be а 4 П, 2 Z' o r 4Z~
s t a t e . The s p i n - o r b i t i n t e r a c t i o n is r e s p o n s i b l e f o r the p r e d i s s o c i a t i o n
and c o n s e q u e n t l y , t h e only n o n - v a n i s h i n g m a t r i x e l e m e n t i s t h a t b e t w e e n
s t a t e s which d i f f e r by o n e o r b i t a l in t h e s i n g l e - c o n f i g u r a t i o n a p p r o x i m a t i o n .
T h e c o n f i g u r a t i o n of t h e A 2 Z+ s t a t e i s « 4 . T h e 4П s t a t e h a s t h e
c o n f i g u r a t i o n с г 7 г с г * , and it can b e shown t h a t
3
<A 2 E1/2 | H s o | 4 П1/2) = 2 a

IAEA - S M R - 1 2 / 4 2 445
w h e r e a= <7г | 2 / ? -H cr*X T h e calculated value i s 56 cm" 1 [64] which can

К
be c o m p a r e d with t h e value f r o m e x p e r i m e n t a l d a t a , 47 cm" 1 .
In t h e c a s e of r o t a t i o n a l p r e d i s s o c i a t i o n s due to the Í-uncoupling
o p e r a t o r , t h e o v e r l a p f a c t o r in Eq. (5.1) is r e p l a c e d by t h e v i b r a t i o n a l f a c t o r
<X, ^ XE X which is r o u g h l y equal to B v <^x v X E /. Such an e x a m p l e a p p e a r s
in t h e H 2 m o l e c u l e , in t h e p r e d i s s o c i a t i o n of t h e D 1 ^ s t a t e (3pcr) by the
B , J E u s t a t e (3pa). As f a r a s the u n i t e d - a t o m s a p p r o x i m a t i o n is valid, the
m o l e c u l a r p a r a m e t e r b = < З р л Г З р с г > = -12 [61].
Few e x a m p l e s e x i s t oî e l e c t r o s t a t i c p r e d i s s o c i a t i o n . O n e i s v e r y
weak and i s due to t h e p r e d i s s o c i a t i o n of t h e R y d b e r g s t a t e Bl,:LEu (4pau)
by t h e R y d b e r g s t a t e В ' 1 ! ^ (3pau) in the s p e c t r u m of the H 2 m o l e c u l e [65].
T h e s e two s t a t e s d i f f e r by one o r b i t a l and it i s not c l e a r which o p e r a t o r is
b e s t suited to study t h i s p r e d i s s o c i a t i o n . In t h e s e two e x a m p l e s c o n c e r n i n g
t h e H 2 m o l e c u l e , both the p r e d i s s o c i a t i n g and t h e p r e d i s s o c i a t e d s t a t e s
have n o n - z e r o t r a n s i t i o n m o m e n t s to the ground s t a t e фо . I n t e r f e r e n c e
e f f e c t s can a p p e a r a s in photoionization and t h e line p r o f i l e h a s an a n t i -
s y m m e t r i c s h a p e c h a r a c t e r i z e d by F a n o ' s index q [66] (see B u r k e ' s p a p e r ,
t h e s e P r o c e e d i n g s ) , but h e r e t h e continuum is that of the n u c l e u s and not
that of the e l e c t r o n as in photoionization e f f e c t s . Using t h e B o r n - O p p e n h e i m e r
f u n c t i o n s , it i s p o s s i b l e to s e p a r a t e t h e e l e c t r o n i c p a r t f r o m t h e v i b r a t i o n a l
factor:
_ 1 <0 l [u 1 Фo> <v I v " )
=
7Г <ф, | H | Ф2><Ф2 | H | * O > < V |VE > < V E I V " >
A n e g a t i v e value f o r q gives a window to the high e n e r g i e s and a p o s i t i v e

value m e a n s a window to the low e n e r g i e s ; q = 0 c o r r e s p o n d s to only one
" e m i s s i o n " line, q = со i s the n o r m a l shape of an a b s o r p t i o n line. T h e sign
of the quantity q depends on the r e l a t i v e sign of all the m a t r i x e l e m e n t s .
As in photoionization, m i x i n g of a d i s c r e t e s t a t e with a continuum s t a t e
r e s u l t s in a l e v e l s h i f t
2
ДЕ V = ^ J Г IHVE-
'E.E ; I dE' (5.2)
where m e a n s that t h e s i n g u l a r i t y i s e l i m i n a t e d f r o m the s u m . T h e e n e r g y

d i s p l a c e m e n t will be v i s i b l e only in s p e c i a l c a s e s [67, 68].
A v e r y s t r o n g p r e d i s s o c i a t i o n r a i s e s t h e p r o b l e m of t h e choice between
t h e two p o s s i b l e a p p r o a c h e s : d i a b a t i c or a d i a b a t i c c u r v e s [69].
The i n t e r a c t i o n can a r i s e t h r o u g h an i n t e r m e d i a t e s t a t e [70] o r o n e
s t a t e i n t e r a c t s weakly with a n o t h e r s t a t e which is a l r e a d y p r e d i s s o c i a t e d
( a c c i d e n t a l p r e d i s s o c i a t i o n ) [71].
The i s o t o p i c e f f e c t in p r e d i s s o c i a t i o n i s v e r y u s e f u l i n h e l p i n g t o
r e c o g n i z e t h e m e c h a n i s m . I f p r e d i s s o e i a t i o n i s due t o t h e r o t a t i o n a l o p e r a t o r , t h e
r a t i o of t h e l i f e t i m e of two i s o t o p i c s p e c i e s i s given roughly by t h e r e c i p r o c a l
s q u a r e of t h e i r r o t a t i o n a l c o n s t a n t s B. F o r e x a m p l e , in the c a s e of
hydrides:
T(XH)
T(XD) L^XHJ
i. e. the l i g h t e s t m o l e c u l e i s m o s t strongly p r e d i s s o c i a t e d [61]. In the

g e n e r a l c a s e , t h e o v e r l a p f a c t o r v a r i e s also with t h e m a s s [58, 64].
6. PREIONIZATIONS
As r e c o m m e n d e d by H e r z b e r g , t h e t e r m " p r e i o n i z a t i o n " i s u s e d h e r e
i n s t e a d of a u t o i o n i z a t i o n to s t r e s s t h e analogy b e t w e e n p r e i o n i z a t i o n and
p r e d i s s o c i a t i o n . H e r e i n t e r a c t i o n t a k e s p l a c e with t h e c o n t i n u u m of t h e
e l e c t r o n i c f u n c t i o n and i s given by
= <фх |н|ф Е ><xv |x'v>

T h e f o r m u l a s f o r Г , q, Л Е a r e t h e s a m e a s f o r p r e d i s s o c i a t i o n e x c e p t
t h a t now фE i s a f u n c t i o n of t h e ion p l u s a f r e e e l e c t r o n .
F o r e x a m p l e , if a d i s c r e t e s t a t e b e l o n g s to a R y d b e r g s e r i e s which
c o n v e r g e s to an e x c i t e d s t a t e of an ion, it c a n i n t e r a c t with t h e continuum
of t h e g r o u n d s t a t e of t h i s ion. T h i s s o r t of p r e i o n i z a t i o n is a r e f l e c t i o n of
h o m o g e n e o u s p e r t u r b a t i o n s b e t w e e n two R y d b e r g s t a t e s c o n v e r g i n g to d i f -
f e r e n t s t a t e s of t h e ion.
T h e s e p r e i o n i z a t i o n s a r e o b s e r v e d in t h e u l t r a v i o l e t v a c u u m s p e c t r u m
o r in t h e photo i o n i z a t i o n c r o s s - s e c t i o n s , a s h a s b e e n shown by B u r k e f o r
a t o m s , but t h e r e e x i s t s an exhibition of t h e s e e f f e c t s p e c u l i a r to m o l e c u l e s
in t h e p h o t o e l e c t r o n s p e c t r u m [72].
P r e i o n i z a t i o n s a r e a l s o o b s e r v e d n e a r t h e t h r e s h o l d , a s in t h e s p e c t r u m
of t h e H2 m o l e c u l e [26] but so f a r no o t h e r i n f o r m a t i o n i s a v a i l a b l e about
t h e width of e a c h r o t a t i o n a l l e v e l and c o n s e q u e n t l y t h e o r i g i n of t h e
m o l e c u l a r p r e i o n i z a t i o n i s not well e x p l a i n e d .
CONCLUSION
In t h i s p a p e r we h a v e t r i e d to show t h a t , though t h e r e p r e s e n t a t i o n of
t h e e l e c t r o n i c w a v e function in t e r m s of one c o n f i g u r a t i o n is not s t r i c t l y
e x a c t , it is v e r y u s e f u l to u n d e r s t a n d t h e p e r t u r b a t i o n and to c h e c k w h e t h e r
t h e p a r a m e t e r s o b t a i n e d by a fit with t h e e x p e r i m e n t a l data h a v e a p h y s i c a l
meaning.
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MURRELL, J . N . , TAYLOR, J . M . , M o l . Phys. 16 (1969) 609.
FIQUET-FAYARD, F . , GALLAIS, O . , M o l . P h y s . 20 (1971) 527.
RAMSAY, D . S . , C H I L D , M . S . , M o l . Phys. 22 (1971) 2 6 3 .
SUTHERLAND, R. A . , ANDERSON, R . A . , J. C h e m . P h y s . 58 ( 1 9 7 3 ) 1 2 2 6 .
C Z A R N Y , J . , FELENBOK, P . , LEFEBVRE-BRION, H . , J . P h y s . В 4 (1971) 124.
HERZBERG, G . , T o p i c s in M o d e r n Physics. A T r i b u t e to Edward U . C o n d o n , C o l o r a d o Ass. U n i v . Press
(1971).
FANO, U . , Phys. Rev. 124 (1961) 1866.
BARDSLEY, J . N . , J. Phys. В 2 (1968) 349.
[68] ATABEK, O . , LEFEBVRE, R . , C h e m . P h y s . L e t t . 17 (1972) 167.

[69] BANDRAUK, A . D . , CHILD, M . S . , M o l . Phys. 19 (1970) 95.
[70] HALL, I . A . , RICHARDS, W . G . , M o l . Phys. 23 (1972) 3 3 1 .
[71] K O V A C S , I . , BUDO, A . , J. C h e m . Phys. 15 ( 1 9 4 7 ) 156.
[72] S M I T H , A . L . , P h i l o s . T r a n s . R. S o c . , London A 2 6 8 (1970) 169.
I A E A - S M R - 1 2 / 3 0 , 31
M U L T I P L E T STRUCTURE OF SPECTRA
O F DIATOMIC MOLECULES
L. KLYNNING
Institute of Physics,
University of Stockholm,
Stockholm, Sweden
Abstract
MULTIPLET STRUCTURE OF SPECTRA OF D I A T O M I C MOLECULES.

1. I n t r o d u c t i o n ; 2 . Basic c o n c e p t s and n o t a t i o n ; 3 . T h e H i l l - V a n V l e c k f o r m u l a ;
3
4. A-type doubling; 5. Z s t a t e s ; 6. Van V l e c k t r a n s f o r m a t i o n ; 1 . C o m p u t a t i o n of r e l a t i v e i n t e n s i t i e s
of r o t a t i o n a l lines; 8. Term value determination.
1. INTRODUCTION
T h e s p e c t r a of d i a t o m i c m o l e c u l e s u s u a l l y e x h i b i t p a t t e r n s t h a t a r e
c h a r a c t e r i s t i c f o r the m o l e c u l e a n d a r e e a s i l y r e c o g n i z e d by v i s u a l i n s p e c t i o n .
T h e t y p i c a l b a n d e d s t r u c t u r e of the s p e c t r u m is p a r t i c u l a r l y n o t i c e a b l e in
s p e c t r o g r a m s t a k e n at low d i s p e r s i o n . R e p r o d u c t i o n s of s u c h s p e c t r o -
g r a m s of a l r e a d y i d e n t i f i e d e m i t t e r s c o l l e c t e d in an a t l a s p r o v i d e a q u i c k
a n d r e l i a b l e m e a n s of i d e n t i f y i n g w h a t d i a t o m i c s p e c i e s a r e p r e s e n t in a
p a r t i c u l a r l i g h t s o u r c e . In o r d e r t o a n a l y s e a n unknown s p e c t r u m , m o r e
p o w e r f u l s p e c t r o g r a p h s a r e n e e d e d . But t h i s i s not e n o u g h , one n e e d s a
t h e o r y , a m o d e l f o r the b e h a v i o u r of the m o l e c u l e . A f t e r t h e f i r s t m a j o r
b r e a k - t h r o u g h in the i n t e r p r e t a t i o n of band s p e c t r a by H e u r l i n g e r (1919)
and e s p e c i a l l y a f t e r the e v e n t of the new q u a n t u m m e c h a n i c s v e r y
c o n s i d e r a b l e p r o g r e s s h a s b e e n m a d e in t h i s f i e l d . At the s a m e t i m e
e x p e r i m e n t a l t e c h n i q u e s h a v e b e e n d e v e l o p e d s o t h a t m o r e and m o r e
d e t a i l s can be d e t e c t e d and new p h e n o m e n a o b s e r v e d . T h e t h e o r y of
d i a t o m i c m o l e c u l e s is t h e r e f o r e b y n o m e a n s in i t s f i n a l s t a t e , a s new
o b s e r v a t i o n s o f t e n r e q u i r e s i g n i f i c a n t c h a n g e s of the t h e o r y .
T h e r e h a s b e e n a c o n s i d e r a b l e i n c r e a s e in the l a s t 5 to 10 y e a r s
in p u b l i c a t i o n s d e a l i n g w i t h t r a n s i t i o n s and m o l e c u l a r s t a t e s w h e r e the
q u a n t u m m e c h a n i c s of t h e old m o d e l s a r e q u e s t i o n e d . T h e new g e n e r a -
t i o n of s p e c t r o s c o p i s t s h a s g r o w n up with q u a n t u m m e c h a n i c s and s e e m s
to h a v e f u l l y a c c e p t e d t h e i d e a s of K r o n i g and o t h e r s f r o m the 1 9 3 0 - i e s
and i s e v i d e n t l y q u i t e c o m p e t e n t to a p p l y t h e s e i d e a s . It i s r e a l i z e d t h a t
o b s e r v a t i o n s w h i c h s e e m at v a r i a n c e with t h e p r e d i c t i o n s of the c u r r e n t
m o d e l could a p p e a r q u i t e n o r m a l w i t h a m o r e r e a l i s t i c and u s u a l l y a l s o
m o r e c o m p l i c a t e d m o d e l . H e r e t h e c o m m o n u s a g e of e l e c t r o n i c c o m -
p u t e r s h a s m a d e it p o s s i b l e to h a n d l e e v e n v e r y c o m p l e x m o d e l s and
n u m e r i c a l l y t e s t d i f f e r e n t a l t e r n a t i v e s on o b s e r v e d d a t a .
T h e o b j e c t of t h e s e l e c t u r e s i s not to show w h e r e we s t a n d e x p e r i -
m e n t a l l y and t h e o r e t i c a l l y t o d a y , but t o give s o m e f a m i l i a r i t y w i t h t h e
c u r r e n t t e c h n i q u e to d e s c r i b e d i a t o m i c m o l e c u l e s , h o p i n g t h a t t h e r e s u l t s
f o u n d in s c i e n t i f i c j o u r n a l s in t h a t w a y w i l l be e a s i e r to p e n e t r a t e .
449
450 KLYNNING
2. BASIC C O N C E P T S AND NOTATION
In o r d e r to d e s c r i b e a m u l t i p l e t s t a t e of a d i a t o m i c m o l e c u l e in
q u a n t u m m e c h a n i c a l t e r m s , we need r e c a p i t u l a t e s o m e b a s i c c o n c e p t s .
T h e c o m p l e t e wave e q u a t i o n of a m a n y - e l e c t r o n m o l e c u l e is an unwieldy
thing in t h e n o n - r e l a t i v i s t i c t h e o r y , and f a r w o r s e in a r e l a t i v i s t i c
t r e a t m e n t . T h e d e t a i l s of how t h i s wave equation is chopped into m a n a g e -
a b l e , but only a p p r o x i m a t e l y c o r r e c t , p i e c e s can be found in, f o r i n s t a n c e ,
K o v á c s , book " R o t a t i o n a l S t r u c t u r e in the S p e c t r a of D i a t o m i c M o l e c u l e s "
[1]. M o s t of the t h e o r e t i c a l r e s u l t s that w i l l be u s e d h e r e a r e in one way
o r a n o t h e r b o r r o w e d f r o m that book. Since a d e t a i l e d knowledge of the
e l e c t r o n i c and s p i n wave f u n c t i o n s i s not e s s e n t i a l to u n d e r s t a n d m u l t i p l e t
s t r u c t u r e , we s t a r t f r o m the H a m i l t o n i a n given by Van V l e c k [3]. Van V l e c k ' s
m e t h o d of " r e v e r s e d " a n g u l a r m o m e n t a , h o w e v e r , r e q u i r e s double
indexing which m a y be c o n f u s i n g s o m e t i m e s . Hougen [4] h a s shown t h a t ,
a p a r t f r o m a p h a s e f a c t o r , the s a m e r e s u l t s can be obtained in a m o r e
s t r a i g h t f o r w a r d w a y . In a NBS m o n o g r a p h [2] Hougen o u t l i n e s in a
p e d a g o g i c a l m a n n e r the i m p l i c a t i o n s of t h i s m e t h o d . Without going into
a l l d e t a i l s t h i s is the m e t h o d that will be u s e d h e r e .
T h e H a m i l t o n i a n f o r the d i a t o m i c m o l e c u l e i s divided into two p a r t s ,
Н = H e v + H r , w h e r e H e v is the H a m i l t o n i a n f o r the n o n - r o t a t i n g m o l e c u l e
and H r i s the r o t a t i o n a l p a r t . Since h e r e we a r e i n t e r e s t e d a l s o in s p i n
i n t e r a c t i o n s , t e r m s c o r r e s p o n d i n g to s p i n - o r b i t , s p i n - s p i n and s p i n -
r o t a t i o n e f f e c t s a r e added s o that our t o t a l H a m i l t o n i a n is w r i t t e n
А Л А A A A
H = Hev + H so + Hss + Hr + HSR
As a b a s i s s e t f o r the n o n - r o t a t i n g m o l e c u l e , we h a v e the (unspecified)

functions
depending on the coupling c a s e at hand. All b a s i s f u n c t i o n s a r e r e f e r r e d to

a m o l e c u l e - f i x e d c o - o r d i n a t e s y s t e m , which in i t s t u r n is r e l a t e d to the
s p a c e - f i x e d c o - o r d i n a t e s y s t e m through the E u l e r i a n a n g l e s ф and 0. The
3 r d angle c/> i s not n e e d e d f o r d i a t o m i c m o l e c u l e s and a f f e c t s the p h a s e of
the wave f u n c t i o n s only. The f u n c t i o n s a r e s u p p o s e d to be s i m p l e
products, i.e.
L S
A L
The n o t a t i o n
L S
A £
and s o on, with the p r o j e c t i o n quantum n u m b e r w r i t t e n below the

c o r r e s p o n d i n g a n g u l a r m o m e n t u m v e c t o r , i s b o r r o w e d f r o m M u s t e l i n [5]
1 A E A - S M R - 1 2 / 3 0 , 37 451
and is of c o u r s e e q u i v a l e n t to Hougen' s n o t a t i o n | LASE)> . Both w i l l be

u s e d in the following. We o b s e r v e t h a t a l l the p r o j e c t i o n q u a n t u m n u m b e r s
h e r e a r e signed q u a n t i t i e s and that Г2 = Л + £ .
F o r the r o t a t i n g m o l e c u l e the above f u n c t i o n s a r e m u l t i p l i e d by a
J
\
f u n c t i o n of the E u l e r a n g l e s Q \ . The p r o j e c t i o n M, which is the
M /
p r o j e c t i o n of the t o t a l a n g u l a r m o m e n t u m J on a s p a c e - f i x e d axis is of
no i n t e r e s t h e r e and w i l l t h e r e f o r e be o m i t t e d . We want to know the
e f f e c t of t h e v a r i o u s a n g u l a r m o m e n t u m o p e r a t o r s when they act upon
o u r b a s i s f u n c t i o n s . F o r c o m p l e t e n e s s the e f f e c t of p a r i t y and t i m e -
r e v e r s a l operators are also listed.
J
J2 J (J + 1)
Q П
J
Jz U = Q
J J
Ji Q = J{J±mJ*Q+l)
fi + 1
л J
ov = (-I)1" n
Q
J J
ÍJ+M-2J
6 Q (-1) -Г2
M -M
L
L = L(L+1)
Л
'L
LZ Л
Л
L L
Л
= J(L + A ) ( L ± Л+1)
Л± 1
L L
= (-1)L"A
Л -A
L
Л -л)
452 KLYNNING
S
= J ( S + E)(S ± E + l)
E± 1
= ("D-i-J
= (-1)2"251 -E
-2T -2SZ
T h e p h a s e f a c t o r s (-1) ' and (-1) in the- 0 - t e r m s of the f i r s t and
t h e l a s t b l o c k s a r e i n t r o d u c e d j u s t to e n s u r e that c o r r e c t r e s u l t s a r e
o b t a i n e d f o r both i n t e g r a l and h a l f - i n t e g r a l m o m e n t a .
Next we c o n s i d e r t h e v a r i o u s p a r t s of the H a m i l t o n i a n e x p r e s s e d in
t e r m s of the a n g u l a r - m o m e n t u m o p e r a t o r s :
Нг = В • R2 where R =J - L - S or
H, = B l f 2 - J 2 + L 2 - L 2 + Š 2 - S2J ДА = Д E = л а = о
+ В [L+Š. + L . Š J ДА = - Д Е = ± 1, ДП = О
- В [L + J_ + L . J + ] ДА = АП = ± 1, Д Е = О
- В [Š + J- + Š . J + ] ДА = О, AU = Д Е = ± 1
л
Й 5 К = у ŘŠ = y ( J - L - Š)Š
c o m p a r e with H t
H s o = > f j i j Sj o r f o r AS = О
AS =±1,0 АЛ = - Д Е = 0 ,
А { LZŠZ + I (L+S. + L . Š + ) }
H s s = e (3Š 2 - Š 2 ) + a ( Š 2 +Š?) + ßS ± (2S z ± 1) ДА = - Д Е = 0, ±1, ±2
B e f o r e we s t a r t t o d e t e r m i n e the m a t r i x e l e m e n t s of t h e s e o p e r a t o r s we
note t h e a n o m a l o u s b e h a v i o u r of J+ and jL c o m p a r e d with t h e n o r m a l
s t e p - u p and s t e p - d o w n o p e r a t o r s L ± and S ± . We a l s o o b s e r v e that the
s i g n of the s q u a r e r o o t i s plus h e r e but m i n u s in, f o r i n s t a n c e , K o v a c s '
b o o k . Since L and S a r e only a p p r o x i m a t e l y good q u a n t u m n u m b e r s we
e x p e c t t h e m a t r i x e l e m e n t s of t h e s e o p e r a t o r s to be s l i g h t l y d i f f e r e n t
f r o m the o n e s l i s t e d . F o r i n s t a n c e
( L 2 - Ц) = L f {L(L + 1) - A 2 }
A
I A E A - S M R - 1 2 / 3 0 , 37 453
3. THE HILL-VAN VLECK FORMULA
A s a f i r s t e x a m p l e , we t r y to r e d e r i v e the f a m o u s H i l l - V a n Vleck
f o r m u l a f o r 2 n s t a t e s . We a s s u m e that with o u r H a m i l t o n i a n H = H e „ + H'
we have m a n a g e d to find a s o l u t i o n to the p r o b l e m H e v | A E , v ^ = En, , | a E , V ) .
H1 is r e g a r d e d a s a p e r t u r b a t i o n and is of the f o r m H = H s o + B R 2 . We
now p r o c e e d t o e v a l u a t e t h e m a t r i x e l e m e n t s of H in t h e s p a c e s p a n n e d by
the f u n c t i o n s | Л Е , T h e q u a n t u m n u m b e r S i s 1 / 2 t h r o u g h o u t and
o m i t t e d in the l a b e l . If we l a b e l the r o w s and c o l u m n s of the m a t r i x s o
t h a t f o r e a c h v a l u e of v the s t a t e s a r e in d e c r e a s i n g o r d e r in the q u a n t u m
n u m b e r Í2, the c o m p l e t e m a t r i x r e p r e s e n t a t i o n of H w i l l look like an
i m m e n s e c h e q u e r b o a r d . Along the m a i n d i a g o n a l we find the block
m a t r i c e s c o r r e s p o n d i n g to e a c h v. P i c k i n g out one of t h e s e and i g n o r i n g
f o r t h e m o m e n t a l l the o t h e r s we obtain
+ 1 + 5. J + I, V + 1 - 5 . J + 2 , V - 1 + 5. J - L V - 1 - 5 . J - 5, V
E
llv + B
vLi
J + 2 *V
+ B v x + 4" (A-2B) - B v -k
0
E B
llv + v L i
1
J+ 1 V
- Bv / x + Bvx - 5 (A-2BV)
Е П у + BLÍ
J - i. V
+ BVX - è ( A - 2 B V ) -Bv Л
0
BL
E
Hv +
1
3
J- 5 V
- B v -fx + Bvx + { (A-2BV)
H e r e x s t a n d s f o r (J + î ) 2 - 1 and L 2 is the value c o r r e s p o n d i n g t o the

operation (L2 - | Л / = L 2 |л)>. T h e r e q u i r e m e n t t h a t e a c h s t a t e should
have a d e f i n i t e p a r i t y i s , h o w e v e r , not f u l f i l l e d . It is p o s s i b l e to c o n s t r u c t
a new b a s i s s e t by a l i n e a r c o m b i n a t i o n of old b a s i s f u n c t i o n s which h a s
the d e s i r e d p r o p e r t y u n d e r a p a r i t y o p e r a t i o n . T h a t i s ctv ф = ± 1 - ф; the
new b a s i s f u n c t i o n s will be denoted by | | л | Q±, J f i , v)>.
I | Л | П ± , J n , v> = — ( | Л Е , Jf2, v / ± | - A - E, J - n , v > )

\T2
T h e t r a n s f o r m a t i o n of the m a t r i x H t o the new b a s e is called a Wang

t r a n s f o r m a t i o n ; it is p a r t i c u l a r l y s i m p l e and e a s y to r e m e m b e r when,
a s in o u r c a s e , the s u b s t a t e s a r e l a b e l l e d in a s c e n d i n g o r d e s c e n d i n g
o r d e r of fi.
454 KLYNNING
In t h i s c a s e it i s i m m e d i a t e l y c l e a r that t h e 4 X 4 m a t r i x can be s p l i t into

two i d e n t i c a l 2 X 2 m a t r i c e s c o r r e s p o n d i n g t o the two e i g e n v a l u e s of the
parity operation.
2 2
n 3 / 2 ± , J 3/2, v n 1 / 2 i , J 1/2, v
, A-2B
E
nv+ 2 - BJx
+ Bx
i A-2B
Il v • 2
- B/x
+ Bx
E = E + B L
where ív nv í x= (J+i)2-l
T h e s o l u t i o n to t h i s s i m p l e s e c u l a r equation is
T(J) = E n v + B v L 2 + B v ( ( J + i ) 2 - 1) ± \ / ( А у " 2 В у ) 2 + B 2 ( ( J + | ) 2 - 1 )
an e x p r e s s i o n that i s r e a d i l y r e c o g n i z e d a s the d e s i r e d H-VV f o r m u l a .

H o w e v e r , the above e n e r g y e x p r e s s i o n i s not v e r y u s e f u l in p r a c t i c a l
a p p l i c a t i o n s . We have t o add c o r r e c t i o n s t h a t take c a r e of f a c t s n e g l e c t e d
s o f a r in o u r H a m i l t o n i a n . T h e m o s t i m p o r t a n t e f f e c t s a r e c e n t r i f u g a l
d i s t o r t i o n t e r m s and Л - t y p e doubling.
Due to the s t r e t c h i n g of the m o l e c u l e when it r o t a t e s , the m o m e n t
of i n e r t i a g r o w s . T h i s could a f f e c t the e n e r g y by s e v e r a l p e r cent at
high J - v a l u e s . A c o r r e c t i o n t e r m - D J 2 (J + l ) 2 o r - D N 2 ( N + 1)2 h a s
f r e q u e n t l y b e e n added to the above H-VV e x p r e s s i o n . F o r 2R s t a t e s which
c o m e c l o s e to the d e s c r i p t i o n given by p u r e Ilund' s c a s e s a o r b, s u c h
a c o r r e c t i o n t e r m could be s u f f i c i e n t , but f o r an i n t e r m e d i a t e - c o u p l i n g
c a s e the f i t t o e x p e r i m e n t a l data is g e n e r a l l y p o o r . A c o r r e c t i o n t e r m
that i s a p p l i c a b l e in the g e n e r a l c a s e c a n e a s i l y be deduced f r o m p u r e l y
I A E A - S M R - 1 2 / 3 0 , 37 455
c l a s s i c a l c o n s i d e r a t i o n s . If the e q u i l i b r i u m i n t e r n u c l e a r d i s t a n c e in the
n o n - r o t a t i n g m o l e c u l e is r e and the r e s t o r i n g f o r c e i s к t i m e s the d i s -
p l a c e m e n t q f r o m r e we can w r i t e f o r the e n e r g y of the n o n - r i g i d r o t a t o r
T h e new e q u i l i b r i u m v a l u e i s d e t e r m i n e d f r o m 3W/9q = 0 which gives
R2
- ~ and thus W=
кцг3 2ßrf 2кцлг'
Making u s e of к = /ни2 we get f o r the c o e f f i c i e n t of Ř 4 : D = 4 B 3 / u 2 ,

known a s K r a t z e r ' s r e l a t i o n . _
Since the m a t r i x e l e m e n t s of R 2 a r e known, it is a s i m p l e m a t t e r of
m a t r i x m u l t i p l i c a t i o n to obtain the d e s i r e d e l e m e n t s of R 4 . In the s a m e
w a y we find c o r r e c t i o n s of h i g h e r p o w e r s of R 2 . It is then i m p o r t a n t to
r e a l i z e that t h e p o t e n t i a l e n e r g y f u n c t i o n i s not a s s i m p l e a s j kq 2 and
t h e r e f o r e i s apt to c o m p l i c a t e the e x p r e s s i o n s . T h e m e t h o d j u s t s k e t c h e d
w a s f i r s t i n t r o d u c e d by A l m y and H o r s f a l l and will in m o s t c a s e s lead to
a s a t i s f a c t o r y r e s u l t (see a l s o Ref. [6]). The s a m e a p p r o a c h , but now
e x t e n d e d to a l l m o l e c u l a r p a r a m e t e r s that can be expanded in p o w e r s e r i e s
in q a r o u n d the e q u i l i b r i u m v a l u e , g a s r e c e n t l y b e e n u s e d by K o v á c s [ 7 , 8 ] .
A d i f f e r e n t m e t h o d b a s e d on p e r t u r b a t i o n t h e o r y h a s b e e n used by m a n y
a u t h o r s , m o s t r e c e n t l y by Hougen (1969) and V e s e t h [9]. In o u r e x a m p l e
we c o n s i d e r e d j u s t one of the block m a t r i c e s H v v along the m a i n d i a g o n a l
c o r r e s p o n d i n g to a s p e c i f i c v i b r a t i o n a l l e v e l . We could take the n e g l e c t e d
o n e s into c o n s i d e r a t i o n by m a k i n g a Van Vleck t r a n s f o r m a t i o n and in that
w a y obtain s e c o n d - o r d e r c o r r e c t i o n s to the e l e m e n t s of H v v . Since both
the r o t a t i o n a l c o n s t a n t B , and the s p i n - o r b i t c o n s t a n t A, a r e f u n c t i o n s of
t h e i n t e r n u c l e a r d i s t a n c e r and t h u s could be e x p r e s s e d a s a p o w e r s e r i e s
of q, we c a n e s t i m a t e t h e i r o f f - d i a g o n a l e l e m e n t s v' |f(q) | v / by u s i n g
h a r m o n i c o s c i l l a t o r wave f u n c t i o n s | v / . It is c u s t o m a r y to do this in
two s t e p s and at f i r s t n e g l e c t the t e r m s o r i g i n a t i n g f r o m A ( r ) . The
r e s u l t i n g c o r r e c t i o n t e r m is a g a i n of the f o r m D R 4 with
l<u|B(r)|v
D
- I E v - E„
U ф V
A s s u m i n g that the i m p o r t a n t c o n t r i b u t i o n s c o m e f r o m the n e i g h b o u r i n g

v i b r a t i o n a l l e v e l s u = v ± 1 one obtains K r a t z e r ' s r e l a t i o n a g a i n .
N o r m a l l y A should be a v e r y s l o w l y v a r y i n g f u n c t i o n of r . In s o m e
c a s e s , h o w e v e r , it i s n e c e s s a r y to c o n s i d e r a l s o t h i s t e r m . J a m e s (1964)
found t h a t a r e p l a c e m e n t A = A v + 2 A j ( J + è) 2 w a s c a l l e d f o r . V e s e t h (1970)
a r r i v e d at a s i m i l a r e x p r e s s i o n and a l s o gave a s i m p l e r e l a t i o n f r o m
w h i c h an e s t i m a t e of Aj could be o b t a i n e d . He found
(Ay+i - A V ) P
A =
J 6B 2 / ы е
456 KLYNNING
T h e r e s u l t s of K o v á c s [7] a r e v e r y m u c h s i m i l a r but a r e g e n e r a l i z e d to
apply to doublet s t a t e s in g e n e r a l . T h i s is f a i r l y s i m p l e to do a s long a s
one s t a y s within t h e s t r o n g l y r e s t r i c t e d b a s i s s e t with j u s t one value of
| Л | . C o n s i d e r i n g that in p r a c t i c a l l y a l l a p p l i c a t i o n s a m o l e c u l a r s t a t e
cannot be looked upon a s i s o l a t e d f r o m the o t h e r s , s u c h a b a s i s s e t i s
r a t h e r u n p h y s i c a l . It i s then not v e r y s u r p r i s i n g that d i f f e r e n t a u t h o r s ,
when d e a l i n g with the c e n t r i f u g a l t e r m s , end up with s l i g h t l y d i f f e r e n t
" f i n a l " e x p r e s s i o n s d e p e n d i n g on when and how a p p r o x i m a t i o n s a r e m a d e .
T h e f o r m u l a given by K o v á c s and V u j i s i c h a s the following f o r m :
T ; ( J ) = T v - j (A]A 2 + y 0 ) + B ' x - D ( x 2 + x - A 2 ) + H x ( x 2 + 3 x + ЗЛ 2 )
where
x = (J + i ) 2 - A 2 , В' = В - A 2 A 2 - a
В* = B' - 2Dx + H ( 3 x 2 + x + A2)
A* = A 0 + A x x + A 2 (x 2 + x - A 2 )
Since t o d a y e l e c t r o n i c c o m p u t e r s a r e u s e d to d e t e r m i n e a l l t h e s e p a r a -
m e t e r s and do it without c o m p l a i n i n g one might think t h a t o u r p r o b l e m s
a r e solved once and f o r a l l . It t u r n s out that i n t e r p r e t i n g the r e s u l t s
b e c o m e s v e r y t r i c k y . F o r i n s t a n c e , when s e v e r a l v i b r a t i o n a l l e v e l s a r e
i n v e s t i g a t e d we m a y obtain v e r y good f i t s f o r e a c h , but with the s m a l l
c o r r e c t i o n c o e f f i c i e n t s changing in a h a p h a z a r d o u s m a n n e r , o r we might
in o t h e r c a s e s find s i m i l a r u n r e a s o n a b l e b e h a v i o u r of c e r t a i n p a r a m e t e r s
when we c o m p a r e i s o t o p i c m o l e c u l e s . E x t e n d i n g the m o d e l by m e a n s of
a d d i t i o n a l r e l a t i o n s b e t w e e n the p a r a m e t e r s is s e l d o m p o s s i b l e , o r e v e n
advisable.
F i g u r e 1 shows r e s u l t s of l e a s t - s q u a r e s fit of the H i l l - V a n Vleck
f o r m u l a t o the t e r m v a l u e s of SnH, with and without c e n t r i f u g a l c o r r e c t i o n
t e r m . As can be s e e n in the d i a g r a m the fit is not v e r y good e v e n with
a D J 2 ( J + l)2 t e r m . With the A l m y - H o r s f a l l f o r m u l a one o b t a i n s s l i g h t l y
s m a l l e r d e v i a t i o n s . Using K o v á c s ' e x p r e s s i o n , the fit i m p r o v e s d r a s t i -
c a l l y . The RMS e r r o r of fit then goes down to 0.04 c m " 1 and the s y s t e m a t i c
e r r o r s in the above d i a g r a m a r e c o m p l e t e l y gone.
4. A - T Y P E DOUBLING
We s e e m to have a r r i v e d at a v e r y s a t i s f a c t o r y m o d e l at l a s t . But
w h a t about the Л-type doubling? Up to now we have c o n s i d e r e d only the
m e a n s of T i c and Tjd . In f a c t we found t h a t t h e s o l u t i o n s of the s e c u l a r
e q u a t i o n gave two e q u a l s e t s of e i g e n v a l u e s and two s e t s of e i g e n f u n c t i o n s
which w e r e d i f f e r e n t u n d e r p a r i t y o p e r a t i o n . T h e r e s e e m s to be no way
of l i f t i n g t h a t d e g e n e r a c y . None of the o p e r a t o r s we have looked at so
f a r could a c c o m p l i s h a s p l i t t i n g of the + and - l e v e l s . T h a t i s , a s long
I A E A - S M R - 1 2 / 3 0 , 37 457
10
E 0
-10 Hvv* DJ2(J*I)2
FIG. 1. L e a s t - s q u a r e s fit of H i l l - V a n Vleck f o r m u l a to t e r m v a l u e s of SnH.
as we s t a y within our o r i g i n a l b a s i s s e t . A d m i t t i n g f u n c t i o n s with A' f A

b r i n g s the L ± o p e r a t o r into a c t i o n and we will s e e that it is this s o called
L - u n c o u p l i n g that is r e s p o n s i b l e f o r the A-type doubling. The t e r m
L - u n c o u p l i n g is u s u a l l y r e s e r v e d f o r i n t e r a c t i o n s l e a d i n g to a c o m p l e t e
d e c o u p l i n g of the o r b i t a l a n g u l a r m o m e n t u m f r o m the i n t e r n u c l e a r a x i s
and to a s t r o n g coupling to the r o t a t i o n a l a x i s , i . e . l e a d i n g to Hund' s
c a s e d. If we look upon the A-type doubling a s a - u s u a l l y s m a l l -
p e r t u r b a t i o n b e t w e e n s t a t e s d i f f e r i n g in A by ± 1 , it is obvious that the
e f f e c t will be a l m o s t none e x c e p t between П and E s t a t e s . All the o t h e r
c o m b i n a t i o n s will c a u s e a s h i f t of the e n e r g y l e v e l s but no s p l i t t i n g . T h i s
is one of the r e a s o n s why E s t a t e s a r e of s p e c i a l i n t e r e s t .
W r i t i n g down our H a m i l t o n i a n again, but now i n s e r t i n g two r o w s and
two c o l u m n s f o r the 2 E s t a t e , one obtains s o m e t h i n g like t h i s :
, 11 „ 1 1 .1 1
22 ° - 2 " 2 J
"^"г J -i-H'
-BL+J.
I
A A
(|A+B)L+S. -BL+J.
A A
- B L . J+ ({A+B) L.Š+ -BL+J-
i
2/ л A
Л л
1 Л A
- B L . J+ (jA+B) L+S. -BL+J-
А л
-BL-J+ (|A+B)L+S-
Л A
- B L . J+
458 KLYNNING
Of c o u r s e , the o p e r a t o r notation L + S_ and so on should be r e p l a c e d by the

c o r r e s p o n d i n g m a t r i x e l e m e n t s , evaluated a c c o r d i n g to the u s u a l r u l e s .
If we now c o n s t r u c t f u n c t i o n s of definite p a r i t y with a Wang t r a n s f o r m a t i o n
t h e m a t r i x w i l l s p l i t into two 3 - b y - 3 b l o c k s , only t h i s t i m e they will not
be i d e n t i c a l .
RJ + ni+ Ei+ Ei. ГЦ. П|-
a a
l аг 4
аз a 5 + a 6
a 7
a
8
a
5 - ae a 4
a
2
аз
a
i
A
a , . a 8 = TE + BE(J+è)(J+è±l) ai = Tn + + Bx
a 4 = - < П | B L + | E> / X a2 = - B / x
l l Л + OR
a s = K n | A L + | E > +<n|BL+|E> a 3 = Tn 5 + Bx
a6 = - < n | B L + | E > (J+l) x = (J + 1 ) 2 - 1
We c a n s e e t h a t t h e e l e m e n t c a l l e d a 6 c o r r e s p o n d i n g to <( 1 - H | - B L - J + 1 0 - ^ - 1 /
c h a n g e s s i g n and t h a t E i + and E^- give d i f f e r e n t d i a g o n a l e l e m e n t s a^ and a B .
When the s i g m a s t a t e is known f r o m o b s e r v a t i o n s , the b e s t p r o c e d u r e
is to s o l v e the s e c u l a r e q u a t i o n s d i r e c t l y . In p r a c t i c e this is s e l d o m the
c a s e and then the a p p r o x i m a t e r o o t s a r e found f r o m s e c o n d - o r d e r p e r t u r b a -
tion c a l c u l a t i o n s , f o r i n s t a n c e by a Van Vleck t r a n s f o r m a t i o n . F o r l a r g e
v a l u e s of A, i . e . when Hund' s c a s e a is a good a p p r o x i m a t i o n , one f i n d s
Ду( 2 ГЦ) % ( p + q ) ( J + i )
(f) (J-£)(J + *)(J+!)
w h e r e a s f o r Hund' s c a s e b one obtains
Д у ( 2 П (b)) » q N (N+l)
The c o e f f i c i e n t p is of the o r d e r 4 А В / у п г and u s u a l l y m u c h l a r g e r than q.

E x p e r i m e n t a l i s t s know t h a t in а 2 П(а) - 2 E t r a n s i t i o n one e x p e c t s to find
l a r g e Л - t y p e doubling only in the 2 ITi - 2 E s u b - b a n d with an a l m o s t l i n e a r
i n c r e a s e of t h e s p l i t t i n g with i n c r e a s i n g J . If a doubling i s d e t e c t e d in the
I A E A - S M R - 1 2 / 3 0 , 37 459
!
E sub-band the splitting should v a r y as the t h i r d p o w e r of J . In
g e n e r a l one e x p e c t s a splitting p r o p o r t i o n a l to J 2 l n l i n Hund' s c a s e a o r
c, but in H u n d ' s c a s e b the splitting is p r o p o r t i o n a l to {N(N + 1)}'AI This
b e h a v i o u r can be u n d e r s t o o d by noting that in o r d e r to lift the d e g e n e r a c y
LS J S J_ L SJ L S J
between — and
•J 2 Л E Q -E •J 2 Л E Q - Л - Е -Г2
L SJ L S J
we need an o p e r a t o r that c o n n e c t s and Since
ЛЕГ? - Л - E -Q
L± Jjf goes j u s t one s t e p in that d i r e c t i o n we m u s t bridge the gap by
c a r r y i n g out 2 I o r 2 | л | s t e p s in o u r p e r t u r b a t i o n c a l c u l a t i o n . This
l e a d s to c o r r e c t i o n t e r m s of the o r d e r B 2 M J 2 M / v 2M_1. v is h e r e s o m e
a v e r a g e d i s t a n c e between the s t a t e s | + M > ^ | М - 1 > , | М - 1 > - | м - 2 > . . .
and M s t a n d s for |s7 | in c a s e a o r с and f o r | a | in c a s e b. To show that,
let u s as an e x a m p l e t r y to e s t i m a t e the Л - t y p e doubling in a *A s t a t e .
We a s s u m e that T ^ D ) = D, Т^П) = P , T ^ E ) = S so that D - P = ui and
P - S = v 2 both a r e much l a r g e r than 2BJ; let a l s o the r o t a t i o n a l p a r t be
included in the T ' s , i . e . T(*A) = Т е у (1Д) + B{J(J + 1) - 4 ) ... We find that
LJ LJ LJ LJ
the m a t r i x e l e m e n t s connecting and and
2 2 1 1 1 1 0 0
s t e m f r o m the - B L ± J + o p e r a t o r . A f t e r m a k i n g a Wang t r a n s f o r m a t i o n ,
we end up with the following m a t r i x H:
D X 0 X = - B [L(L+1) - 2]i • [ J ( J - l ) ] *
X P Y Y = - В [L(L+l)]i [J(J+l)]i
O Y S with D » P » S
H
P X
X D
Removing the S t e r m via second o r d e r p e r t u r b a t i o n we get two m a t r i c e s
D X D X
and
X P + X P
The d i f f e r e n c e between the root Dj and is a p p r o x i m a t e l y
X" X" X 2 Y2
v\v2
vi -
V2
|2Q|
Av(iA) - ж const ifji
'1 "2 '1 "2
F o r s t a t e s with S s 1 the s p i n - s p i n o p e r a t o r w i l l a l s o contribute to the splitting.
It is obvious that since the E s t a t e c a u s e s a splitting of the d e g e n e r a t e
X-components in the Г: s t a t e a s i m i l a r splitting in the E s t a t e will a p p e a r .
A c c o r d i n g to Van Vleck this is the m a i n contribution to the spin splitting
of s i g m a - t e r m s . Unlike s t a t e s with | л | f 0 which a r e twofold d e g e n e r a t e ,
460 KLYNNING
s i g m a - s t a t e s will s p l i t e v e n in the a b s e n c e of o t h e r p e r t u r b i n g s t a t e s .
T h i s f i r s t - o r d e r t e r m i s , h o w e v e r , l e s s i m p o r t a n t than the s e c o n d - o r d e r
t e r m a r i s i n g f r o m the Е-Г1 i n t e r a c t i o n . We can t h e r e f o r e e x p e c t that p
and y a r e of the s a m e m a g n i t u d e .
I n d e e d , if we s o l v e the c o m p l e t e 3 - X - 3 s e c u l a r equation f o r both +ve
and - v e l e v e l s and a f t e r w a r d s e x p r e s s the e n e r g y of the 2 E l e v e l s with the
c o n v e n t i o n a l c a s e b a n g u l a r m o m e n t u m N i n s t e a d of J we find that the two
l e v e l s F i ( N ) and F2(N), which without p e r t u r b a t i o n w e r e a l m o s t c o i n c i d e n t ,
now have s e p a r a t e d with a AVI 2 (N) = y • (N + -§) w h e r e |Y| « p in 2 n .
A l m o s t c o i n c i d e n t , b e c a u s e t h e r e is, in g e n e r a l , a f i r s t - o r d e r e f f e c t f r o m
H SR of the s a m e f o r m , i . e . Д v(N) = y' ( N + | ) , but w h e r e 71 u s u a l l y i s m u c h
l e s s than the y c o m i n g f r o m the p e r t u r b a t i o n with 2П .
The t e r m f o r m u l a f o r a 2 E s t a t e is e a s i l y d e r i v e d
T i , 2 ( N ) = T t v - I + BN(N+1) - DN 2 (N+1) 2 ± | (N+Í)
f o r TI we have J = N + i and f o r T 2 l e v e l s J = N - i . An a l t e r n a t i v e r o t a t i o n
is TJ±I(N) with TJ.I(N) ЕЕ T ^ N ) .
T h e d e s c r i p t i o n of doublet s t a t e s we have r e a c h e d s o f a r is p r o b a b l y
s u f f i c i e n t l y good f o r p r a c t i c a l n e e d s in c o n v e n t i o n a l band s p e c t r o s c o p y .
In f a c t it is a m a z i n g l y good, r e m e m b e r i n g t h a t we s t a r t e d with a v e r y
r e s t r i c t e d b a s i s , i n d e e d . With the new e x p e r i m e n t a l t e c h n i q u e s , s u c h a s
l e v e l c r o s s i n g e x p e r i m e n t s , Hanle e f f e c t , o p t i c a l double r e s o n a n c e and
s o on, the c h a n c e s a r e t h a t the t h e o r y should be a m e n d e d . It d o e s not
s e e m p o s s i b l e to find g e n e r a l f o r m u l a s f o r e a c h s t a t e that m e e t t h i s new
d e m a n d , s o m a y b e the solution is t a i l o r - m a d e t h e o r y f o r s p e c i f i c p r o b l e m s .
d
5. E STATES
As a s e c o n d e x a m p l e we c o n s i d e r a 3 E s t a t e . , Sigma s t a t e s a r e
u s u a l l y said to f a l l c l o s e to Hund 1 s c a s e b. T h i s is s o b e c a u s e the s p i n -
o r b i t i n t e r a c t i o n ALS g i v e s no contribution and the s p i n - s p i n t e r m in m o s t
c a s e s is n e g l i g i b l e . But in quite a few c a s e s , e s p e c i a l l y in h e a v y m o l e -
c u l e s , l a r g e d e v i a t i o n s f r o m a Hund' s c a s e b d e s c r i p t i o n have b e e n found.
In A s H the 3 E~ s t a t e h a s a s e p a r a t i o n b e t w e e n the 1 and the 0 + l e v e l s of
n e a r l y 120 c m " 1 , in BiH it is 4900 c m " 1 . The s e p a r a t i o n b e t w e e n the 1/2
and 3 / 2 c o m p o n e n t s of the 4 E~ s t a t e in SnH is 274 cm" 1 and in P b H the
s e p a r a t i o n i s e x p e c t e d to be much l a r g e r . F o r s u c h c a s e s one
o b v i o u s l y h a s to c o n s i d e r not only the i n t e r a c t i o n s " w i t h i n " the spin
m u l t i p l e t i t s e l f but a l s o to e s t i m a t e the i n f l u e n c e f r o m o t h e r e l e c t r o n i c
states.
But h e r e we s t a r t with an i s o l a t e d 3 E s t a t e . R e s t r i c t i n g o u r b a s i s
s e t to the f u n c t i o n s ^ ^ y i , E = Q = 0, ±1 and u s i n g the H a m i l t o n i a n
H r given e x p l i c i t l y we can i m m e d i a t e l y w r i t e down i t s m a t r i x . We do not
c o n s i d e r r o t a t i o n a l d i s t o r t i o n c o r r e c t i o n s , but of c o u r s e this h a s to be done
b e f o r e one t r i e s to apply the r e s u l t on a c t u a l d a t a . The m e t h o d i s e n t i r e l y
a n a l o g o u s to what we did b e f o r e in the doublet c a s e .
I A E A - S M R - 1 2 / 3 0 , 37 461
01 l j OOOJ £ 3 v + £
0-1-1J 1± 1+
T+£ - у T+е - у
•J2ŠŠ
+ Вй* - К + BSř
Т - 2е - 2у T - 2с - 2у
Г у] Г у] =>
Г г!
- в - 4- Ш? -[В"2 -2LB2 J ^
L J + В [£"+ 2] + В(^+ 2)
Т+ t-у Т + £ -у
+
•[••Я + BSř
S ř = J(J+1)
F o r s y m m e t r y o p e r a t i o n s on the f u n c t i o n s
L 1 J lb 1 J L 1 J \ L 1 J \
0 1 1 0 -1-1 L 1 J 0 11 / 0 -1 - 1 /
and
•Í2 0 0 0 Л
s e e J . T . Hougen' s m o n o g r a p h (Section 2).
F o r a 3 E~ s t a t e , putting X = 3 e / 2 , T'= T + e - 7 and i f = J(J+1) we find
T 1 + В J ( J + 1)
T' + BÄ" - X - В + ^ J ± . X /(2B- 7 ) V + (X - В + 2

o±
We s e e that if X is m a d e l a r g e (positive o r negative) 3E~i- and 3 E j +

w i l l c o m e c l o s e t o g e t h e r with a s e p a r a t i o n p r o p o r t i o n a l to J ( J + 1 ) , i . e . they
w i l l look like a i n s t a t e , while thè 3 EJ+ c o m p o n e n t is f a r away and t a k e s
+
t h e f o r m of a state.
If we r e p l a c e J in the e n e r g y e x p r e s s i o n s by N, N ± 1 we obtain the
f o r m u l a by M i l l e r and T o w n e s :
T j (N) = T 2 (N) + В (2N+3) - ( x - B + ^ - f (N+l)
T 2 (N) = T + e - 7 + BN(N+1) - D N 2 ( N + 1 ) 2
T 3 (N) = T 2 ( N ) - В (2N-1) - ( x - B + + f(N-l)
with
2 4 1/2
f(N) = -j (2B - 7) 2 N(N+1) + ( X - B + l
T o s e e how n e i g h b o u r i n g s t a t e s might a f f e c t the r e l a t i v e e n e r g i e s of

3
the E " s t a t e we m u s t extend the b a s i s s e t , m a k i n g r o o m f o r 3 П , and
462 KLYNNING
1
E + . The m a t r i x then o b t a i n e d can be s p l i t into one m a t r i x f o r the e v e n
l e v e l s and one f o r the odd l e v e l s . A f t e r d i a g o n a l i z a t i o n we c a n d i s r e g a r d
a l l e i g e n v a l u e s e x c e p t t h o s e belonging to 3 E .
A m u c h m o r e convenient m e t h o d , at l e a s t when the i n t e r a c t i n g s t a t e s
a r e not w e l l known, is to r e d u c e the p r o b l e m by applying a Van Vleck
transformation.
6. VAN V L E C K TRANSFORMATION
Й = Й 0 + XHi + X 2 H 2 . The m a t r i x of H 0 is d i a g o n a l : = ó ^ E j
i j к m , n ...
If we a r e only i n t e r e s t e d in the s h a d e d p a r t of the H - m a t r i x , let the

r u n n i n g i n d i c e s within t h a t block be i, j , к and in the u n i n t e r e s t i n g o u t s i d e
b l o c k n , m . Define a m a t r i x T = e i X S by the e x p a n s i o n T = I + iXS - \ X 2 S 2 + ...
and T " 1 = I - iXS - j X 2 S 2 - ... . The t r a n s f o r m e d m a t r i x H' = T" 1 H T can
be w r i t t e n H' = H + i X [ H ь S] - | X2 [[ H, S], S] o r , a f t e r c o l l e c t i n g t e r m s
with the s a m e p o w e r in X
H' = H 0 +iX{ H ; + [ H 0 , S ] } + X2 (H 2 + i [ H i , S] - | [ [ H 0 , S ] , S]) + ...
C h o o s e S so t h a t < j [HJ + [Ho, S] | n O = 0 f o r all j and m and f u r t h e r

•(j |S = <(m |S | n > = 0 f o r a l l j , к and m , n.
S =
T h e n < j IS I m / = i
We find f o r the e l e m e n t | H1 |k \/ .
•
О|н1|к>=О|н0+хн.1 + х2н2|к> + Н 2
УZ-I ( E i +
^-rTlg
(bj - E m ) (Ek
| H l
-
h
Em)
) < m | H l | k >
I A E A - S M R - 1 2 / 3 0 , 37 463
We s e e t h a t the m a i n d i f f e r e n c e between t h i s m e t h o d and o r d i n a r y 2nd-

o r d e r p e r t u r b a t i o n s is that a l l e l e m e n t s within the s e l e c t e d b l o c k , and not
j u s t the d i a g o n a l o n e s , a r e c o r r e c t e d f o r i n f l u e n c e f r o m o u t s i d e t h i s b l o c k .
When a l l the e l e m e n t s i n s i d e the diagonal block u n d e r c o n s i d e r a t i o n
a r e c o r r e c t e d by t h i s p r o c e d u r e one obtains a new s e c u l a r e q u a t i o n to be
s o l v e d . In the e x a m p l e s given so f a r , it h a s b e e n p o s s i b l e to c a l c u l a t e the
n e c e s s a r y m a t r i x e l e m e n t s in a r a t h e r m e c h a n i c a l w a y . In m a n y c a s e s ,
h o w e v e r , the n u m b e r of unknown p a r a m e t e r s that m u s t be d e t e r m i n e d f r o m
e x p e r i m e n t a l d a t a is too l a r g e f o r a d i r e c t s o l u t i o n of the s e c u l a r e q u a t i o n .
The m a t r i x f o r m u l a t i o n of the p r o b l e m is then of g r e a t a d v a n t a g e , s i n c e by
m e r e i n s p e c t i o n , l i n e a r d e p e n d e n c e s b e t w e e n p a r a m e t e r s m a y be
d e t e c t e d and r e m o v e d . If a d d i t i o n a l i n f o r m a t i o n i s a v a i l a b l e , a s f o r
i n s t a n c e H a r t r e e - F o c k e s t i m a t e s , s o m e p a r a m e t e r s m i g h t be r e p l a c e d
by t h e s e a p p r o x i m a t e v a l u e s and so making the s e c u l a r equation t r a c t a b l e .
E n e r g y e x p r e s s i o n s in the c l o s e d f o r m a r e e v i d e n t l y l e s s s u i t e d f o r s u c h
a d j u s t m e n t s . T h e n e e d f o r s u c h c l o s e d - f o r m e x p r e s s i o n s is a l s o q u e s t i o n -
a b l e . N o w a d a y s , c o m p u t e r s of s o m e kind would be u s e d both to e v a l u a t e the
c l o s e d - f o r m f o r m u l a s and to d i a g o n a l i z e the H a m i l t o n i a n m a t r i x .
4
6.1. E n e r g y m a t r i x f o r E states
It m a y be s u r p r i s i n g t h a t the Hund' s c a s e a b a s i s s e t i s u s e d a l s o
f o r E s t a t e s . In m o s t c a s e s a b a s i s s e t c o r r e s p o n d i n g to Hund' s c a s e b
s e e m s like a b e t t e r a p p r o x i m a t i o n . The f a c t i s that in m o s t c a s e s m e t
with in p r a c t i c e , the c a s e a' ( a c c o r d i n g to Kopp and Hougen) m a t r i c e s a r e
e a s i e r to h a n d l e . If a c o m p u t e r is u s e d to s o l v e the s e c u l a r e q u a t i o n
n u m e r i c a l l y it is e a s y to give t h e t r a n s f o r m a t i o n m a t r i x should it be
n e e d e d . In c a s e s w h e r e it i s n e e d e d , a s f o r i n s t a n c e when the i n t e n s i t i e s
of the l i n e s a r e c o n s i d e r e d , then we m o s t c e r t a i n l y w i l l let the c o m p u t e r
do the m a n i p u l a t i o n s .
The q u a r t e t s i g m a s t a t e h a s b e e n d i s c u s s e d f r o m a t h e o r e t i c a l point
of view on m a n y o c c a s i o n s , but not v e r y m a n y e x a m p l e s have b e e n found
e x p e r i m e n t a l l y . A d e t a i l e d a c c o u n t of the v a r i o u s i n t e r a c t i o n s t h a t m a y
o c c u r h a s r e c e n t l y b e e n given by Ko v a c s .
O t h e r t y p e s of s t a t e s c a n a l s o be w o r k e d out with the t e c h n i q u e we have
used here.
7. C O M P U T A T I O N O F R E L A T I V E INTENSITIES O F ROTATIONAL
LINES
The p i c k i n g out of b r a n c h e s , although it could be done by a c o m p u t e r ,

i s m o s t e a s i l y m a d e by h a n d . It is quite o b v i o u s t h a t the d i s t r i b u t i o n of
i n t e n s i t y a m o n g the v a r i o u s b r a n c h e s and a l s o within a b r a n c h of a band
i s one of the f a c t o r s t h a t h e l p s u s to r e c o g n i z e the p a t t e r n s so q u i c k l y .
W o r k i n g with wave n u m b e r s only would be a v e r y d i f f i c u l t way of a n a l y s i n g
a band.
F o r the p u r p o s e of finding a c o r r e c t a n a l y s i s only, it i s s u f f i c i e n t to
know the r e l a t i v e line i n t e n s i t i e s . T h e e l e c t r o n i c t r a n s i t i o n p r o b a b i l i t i e s ,
which a r e d i f f i c u l t to o b t a i n , can then be i g n o r e d and f o r the s a m e r e a s o n
we do not have to c o m p u t e the F r a n c k - C o n d o n f a c t o r s ; t h i s , h o w e v e r , can
be done at the f i n a l s t a g e of the a n a l y s i s .
464 KLYNNING
We know t h a t t h e i n t e n s i t y of an e l e c t r i c d i p o l e t r a n s i t i o n ( p o l a r i z e d
in the Z - d i r e c t i o n ) c a n be w r i t t e n a s Iif °° |<(f |/uz | 0 | 2 e x P ( _ E i / k T ) if
in a d d i t i o n we a l s o a s s u m e t h e r m a l e q u i l i b r i u m .
T h e s e l e c t i o n r u l e f o r d i p o l e t r a n s i t i o n s , w h i c h we find f r o m the
s y m m e t r y p r o p e r t i e s of Д, i s +** - , and in c a s e of h o m o n u c l e a r m o l e c u l e s
a l s o a <-1-> s . S i n c e o u r w a v e f u n c t i o n s a r e r e l a t e d to the m o l e c u l e - f i x e d
c o - o r d i n a t e s w e m u s t f i n d t h e c o m p o n e n t s of in t h i s s y s t e m . We h a v e
n z = ffzzn2 + j(az+ ß- + az.ß + ) w h e r e a x k i s the d i r e c t i o n - c o s i n e m a t r i x .
F r o m t h e /u^ w e o b t a i n t h e s e l e c t i o n r u l e s E + * E~ and g «—1• u. If the щ
a r e i n d e p e n d e n t of s p i n , i . e . w h e n Hund' s c a s e a i s a good a p p r o x i m a t i o n
w e f i n d t h a t t h e only n o n - v a n i s h i n g e l e m e n t s of t h e m a t r i x
L' S L S
Л' E 1 Л E
m u s t be of the f o r m
q = 0 , ±1 (Mo = M z)
\A+q
T h e v a l u e s of t h e s e e l e m e n t s a r e to be d e t e r m i n e d f r o m e x p e r i m e n t s .
H o w e v e r , w i t h t h e h e l p of the s y m m e t r y o p e r a t i o n s crv and в t h e i r n u m b e r
m i g h t be r e d u c e d . F r o m the f o r m of p z i n the m o l e c u l e - f i x e d s y s t e m it
LS 4
is c l e a r that, as long as is s e p a r a b l e into a n o r b i t a l p a r t and a
Л E
s p i n p a r t , we c a n h a v e e i t h e r p a r a l l e l t r a n s i t i o n s o n l y (mz)> o r o n l y
perpendicular transitions
In o r d e r to c o n s t r u c t the d i p o l e - m o m e n t m a t r i x we n e e d the m a t r i x
e l e m e n t s of aZY • W r i t i n g f o r c o n v e n i e n c e u z ~ ßoMz + ß+M- + ß-M + w e
find t h a t ß d e p e n d s on A J = J 1 - J " ; so we o b t a i n d i f f e r e n t f a c t o r s f o r t h e
R , Q and P b r a n c h e s . S u m m i n g o v e r a l l M o n e o b t a i n s :
R Q P
(J + l - f 2 ) ( J + l + n ) Q j 2J+1 Rj-Q)(j+Q)
3(J + 1) ^ 3 J ( J + 1) V 3J
nj+^+l)(J+n+2) I (J+ fž)(J ± Q+1)(2J + 1) _ f ( J ± Q ) ( J ± n - 1)

+
V 6(J + 1) V 6 J ( J + 1) V 6J
Note t h a t t h e s i g n s of the R and P a m p l i t u d e s f o r А Л = ± 1 t r a n s i t i o n s a r e

d i f f e r e n t . If e i t h e r t h e u p p e r o r the l o w e r s t a t e i s p e r t u r b e d by a s t a t e
h a v i n g А Л = ± 1 one m a y h a v e l a r g e i n t e n s i t y a n o m a l i e s , b e c a u s e t h e n the
a m p l i t u d e s of both s t a t e s h a v e to be a d d e d b e f o r e the i n t e n s i t y i s c a l c u l a t e d .
If the p e r t u r b a t i o n i s s t r o n g and the d i p o l e m o m e n t s h a v e the r i g h t m a g n i t u d e s
a w h o l e b r a n c h ( f o r i n s t a n c e t h e R b r a n c h ) c a n b e m i s s i n g w h i l e the o t h e r
(e.g. P) b r a n c h gets much h i g h e r intensity.
We c a n now c o n s t r u c t a l l the m a t r i c e s we n e e d . By d i a g o n a l i z i n g the
H a m i l t o n i a n of t h e u p p e r s t a t e we find f o r U: U _ 1 H u p p e r U = E u p p e r .
S i m i l a r l y , we f i n d f o r L : L'iHiower L = E i o w e r .
I A E A - S M R - 1 2 / 3 0 , 37 465
D(R), D(Q), D(P) a r e c o n s t r u c t e d with the help of the m a t r i x e l e m e n t s

of the d i r e c t i o n c o s i n e s . If we give a n ' a r b i t r a r y v a l u e to ß {/^n and ß±)
a l l t h e s e c a l c u l a t i o n s can be m a d e by a c o m p u t e r f o r a l l J - v a l u e s of
interest.
T h e i n t e n s i t i e s a r e then obtained a s
I i f = c o n s t X exp ( - E initiai / k T ) | <f | U"!D(Aj) L | i > | 2
8. T E R M VALUE D E T E R M I N A T I O N
T h e two t r a n s i t i o n s i l l u s t r a t e d in F i g . 2 , A - X and B - X , can be u s e d

to e x e m p l i f y a m e t h o d t h a t h a s b e c o m e m o r e and m o r e u s e d in s p e c t r o -
s c o p i c l a b o r a t o r i e s to d e t e r m i n e a " b e s t " s e t of t e r m v a l u e s f r o m the
o b s e r v e d wave n u m b e r s of the l i n e s . It i s not d i f f i c u l t to m a k e the g u e s s
that the " t e r m - v a l u e m e t h o d " w i l l be a l e a s t - s q u a r e s p r o c e d u r e , but it
m a y be a l i t t l e m o r e d i f f i c u l t to s e e how one a c t u a l l y can s o l v e the r e s u l t i n g
o v e r d e t e r m i n e d s y s t e m of e q u a t i o n s .
Since f o r any s p e c t r a l line Wjf we have W;f = Tj - T f , it is p o s s i b l e
to r e p r e s e n t all o b s e r v e d l i n e s in MX = W. T h e m a t r i x M m a y have
d i m e n s i o n s of the o r d e r 15 000 X 5000, so a d i r e c t b r u t e - f o r c e method
is c l e a r l y u n s u i t a b l e . If we o b s e r v e that m o s t e l e m e n t s of M a r e z e r o
and that the two n o n - z e r o e l e m e n t s of e a c h row can only be +1 o r - 1 , we
r e a l i z e that t h e r e m u s t be a way of taking a d v a n t a g e of this f a c t . T h i s
c a n be done by r e m e m b e r i n g t h a t c o m p u t e r s r e a l l y like it to do dull
c o m p u t a t i o n s o v e r and o v e r again; we have to p r e s e n t d a t a in a f o r m that
r e p e a t s itself f r o m the c o m p u t e r s ' point of view. We can a l s o take
a d v a n t a g e of the f a c t t h a t f o r dipole t r a n s i t i o n s not a l l c o m b i n a t i o n s Tj ,
Tf a r e p e r m i t t e d .
We take all identified l i n e s and c o m p i l e t h e m in a t a b l e , one c o l u m n
f o r e a c h b r a n c h , and with the r o w s n u m b e r e d e i t h e r by the r o t a t i o n a l
q u a n t u m n u m b e r , if the a b s o l u t e n u m b e r i n g i s known, o r by a r e l a t i v e
n u m b e r i n g . Since t h i s n u m b e r i n g could be s t a r t e d e i t h e r f r o m the u p p e r
P 0 R P Q R
- 3
- 2
— 1
FIG. 2 . T r a n s i t i o n s A - X and B-X c o n s i d e r e d in t e r m v a l u e d e t e r m i n a t i o n .

466 KLYNNING
s t a t e o r f r o m the l o w e r s t a t e we have to m a k e a c h o i c e . T h e e q u a t i o n s
MX = W c a n now be w r i t t e n { vs = a T A j - bT B }, j = 1, ... j m a x , i . e . we
t a k e one r o w at a t i m e .
-1
Al B.J-l
A2
-1 B,J
A3
B, J+l
-1
To s o l v e the l e a s t - s q u a r e s p r o b l e m we need M T M X = M T W . We s t a r t
to c o n s t r u c t M T M by doing a s much a s p o s s i b l e with the s i n g l e row
a T a and b T b a r e at f i r s t d i a g o n a l . We e l i m i n a t e b T a , and t h e n b T b
i s no l o n g e r d i a g o n a l . The l e f t - h a n d s h a d e d block c a n , h o w e v e r , be
s i m p l i f i e d y e t . We can e l i m i n a t e all n o n - z e r o e l e m e n t s e x c e p t t h o s e
along the m a i n d i a g o n a l , w h e r e we a r r a n g e t h e m so that we o b t a i n only
o n e ' s . T h e r e s t of the m a t r i x we cannot t o u c h , b e c a u s e w h e n a next row
of d a t a i s c o m i n g in, it w i l l a l t e r b r b a s c a n be s e e n by the dotted blocks
in F i g . 3 .
But b e f o r e we go on with t h e next r o w , we s t o r e a w a y the two u p p e r -
m o s t b l o c k s of b T b on the r i g h t - h a n d s i d e to s o m e o t h e r p l a c e and s h i f t
a l l o u r r e m a i n i n g e l e m e n t s of b T b in p o s i t i o n . The s i t u a t i o n i s now, f r o m
J-1 J J-1 >2
-i
i
i
L J
bV bTa " "1 i

1
1
1
Щ
"/Л
1 b'b
1 L- _
FIG. 3 . S c h e m a t i c r e p r e s e n t a t i o n of m a t r i x used in l e a s t - s q u a r e s c o m p u t a t i o n .
I A E A - S M R - 1 2 / 3 0 , 37 467
the c o m p u t e r ' s point of v i e w , e x a c t l y the s a m e a s when we s t a r t e d . T h i s

p r o c e d u r e i s then r e p e a t e d until the l a s t row i s r e a d . We do not need to
s t o r e a w a y a p a r t of b T b s i n c e the e q u a t i o n s r e p r e s e n t e d by b T i / j m a x гЬ^ЪТв
can be solved d i r e c t l y .
We can now go b a c k w a r d s s t e p by s t e p and c o l l e c t the l a s t s t o r e d
p a r t , e l i m i n a t e , and o b t a i n all the T B and a l s o a l l T A .
T h e r e is one d i f f i c u l t y only. Since a l l e q u a t i o n s a r e d i f f e r e n c e s
b e t w e e n two u n k n o w n s , the l a s t b T b m u s t be s i n g u l a r . T h i s i s o v e r c o m e
by a s s i g n i n g an a r b i t r a r y value to one of the T B , i . e . we add one e q u a t i o n
which f i x e s the e n e r g y s c a l e .
With the t e r m v a l u e s d e t e r m i n e d in the above m a n n e r it i s e a s y to
c o m p u t e the r e c o n s t r u c t e d line f r e q u e n c i e s and obtain the RMS d e v i a t i o n .
F o r d e t a i l s s e e R e f s [10] and [11].
REFERENCES
[1] KOVACS, 1., R o t a t i o n a l S t r u c t u r e in t h e S p e c t r a of D i a t o m i c M o l e c u l e s , A . H i l g e r Ltd. ( 1 9 6 9 ) .

[2] HOUGEN, ] . T . , T h e C a l c u l a t i o n of R o t a t i o n a l Energy L e v e l s a n d R o t a t i o n a l Line I n t e n s i t i e s in
Diatomic Molecules, NBS M o n o g r a p h ( 1 9 1 0 ) 1 1 5 .
[3] VAN VLECK, J . H . , Rev. M o d . Phys. 2 3 ( 1 9 5 1 ) 2 1 3 .
[4] HOUGEN, J. T . , J . C h e m . Phys. 36 ( 1 9 6 2 ) 5 1 9 .
[5] MUSTEUN, N . . T h e s i s , Âbo (1963).
[6] ROSTAS, J . , T h e s i s , Paris ( 1 9 6 8 ) .
[7] KOVACS, J . , J. Phys. В 4 , (1971) 7 5 9 , 1 1 2 3 , 1633.
[8] K O V A C S , J . , A c t a Phys. A c a d . Sei. H u n g . 32 ( 1 9 7 2 ) 5.
[9] VESETH, L . , T h e s i s , Oslo (1971).
[10] ASLUND, N . . A r k . Fys. 30 (1965) 3 7 7 .
[11] ÄSLUND, N . . A r k . Fys. 30 (1965) 153.
P A R T III: COLLISIONS
IAEA - S M R - 1 2 / 1 4
A T O M I C COLLISION T H E O R Y
B.L. MOISEIWITSCH
Department of Applied Mathematics and Theoretical Physics,
Queen's University of Belfast,
Northern Ireland, United Kingdom
Abstract
A T O M I C COLLISION THEORY.
1. S c a t t e r i n g by a c e n t r a l p o t e n t i a l ; 2. Variational m e t h o d s ; 3 . Elastic s c a t t e r i n g of e l e c t r o n s by
atoms; 4 . E x c i t a t i o n of a t o m s by e l e c t r o n i m p a c t ; 5. R e s o n a n c e s .
1. SCATTERING B Y A C E N T R A L P O T E N T I A L
1.1. Cross-sections
L e t u s c o n s i d e r a b e a m of p a r t i c l e s i n c i d e n t along t h e d i r e c t i o n of t h e
z - a x i s on a s c a t t e r i n g c e n t r e s i t u a t e d at t h e o r i g i n . If N p a r t i c l e s p e r
s e c o n d c r o s s t h e unit a r e a p e r p e n d i c u l a r to t h e b e a m , the n u m b e r of
p a r t i c l e s d e f l e c t e d p e r second t h r o u g h a n g l e s 6, ф into t h e solid a n g l e
e l e m e n t dio m a y b e w r i t t e n
N1(0, ф) du (1)
Since t h i s quantity h a s t h e d i m e n s i o n s of i n v e r s e t i m e , 1(0, Ф) h a s t h e

d i m e n s i o n s of a r e a and i s c a l l e d t h e d i f f e r e n t i a l c r o s s - s e c t i o n .
I n t e g r a t i n g o v e r a l l solid a n g l e s y i e l d s t h e t o t a l c r o s s - s e c t i o n
Q = / I(e,<fr)dw (2)
t h e t o t a l n u m b e r of p a r t i c l e s s c a t t e r e d p e r s e c o n d f r o m an i n c i d e n t b e a m
of unit f l u x .
We s u p p o s e t h a t t h e p a r t i c l e s of t h e i n c i d e n t b e a m h a v e m a s s m and
i n i t i a l s p e e d v. T h e n , we can r e p r e s e n t t h e m by the p l a n e wave
Aeikz (3)
w h e r e к = m v / f i = 2n/X i s t h e wave n u m b e r and X i s t h e de B r o g l i e wave

length.
Now, t h e c u r r e n t d e n s i t y j f o r t h e wave f u n c t i o n ф i s given by
H e n c e , the f l u x of i n c i d e n t p a r t i c l e s i s v | A | 2 s o that A = V N / v .
471
472 MOISEIWITSCH
F o r l a r g e d i s t a n c e s r f r o m the o r i g i n , the s c a t t e r e d p a r t i c l e s m a y
b e r e p r e s e n t e d b y t h e outgoing s p h e r i c a l wave
A„ikr
ае.ф) (5)
w h e r e f(0, ф) i s c a l l e d the s c a t t e r i n g a m p l i t u d e .
It f o l l o w s that t h e r a d i a l flux is
v]A] 2 |f(0, ф)| 2

(6)
so that
Кб, Ф) = |f(e, ф)\ (7)
C o m b i n i n g the i n c i d e n t wave with the s c a t t e r e d wave y i e l d s
A { e i k z + - e i k r f(9, ф)} (8)

r
f o r t h e a s y m p t o t i c f o r m of t h e wave f u n c t i o n a s г -> » ,
We s h a l l s u p p o s e t h a t v p a r t i c l e s c r o s s t h e unit a r e a p e r s e c o n d so
t h a t A = 1.
1.2. I n t e g r a l equation f o r s c a t t e r i n g a m p l i t u d e
T h e s c a t t e r i n g of p a r t i c l e s with e n e r g y E = ii2 k 2 / 2 m by a c e n t r a l
p o t e n t i a l V(r} i s d e t e r m i n e d by the S c h r ö d i n g e r equation
k2 - ^ f У Й Ж ? ) =0 (9)
where
ф{r) + r " J e i k r f(0, Ф) (10)
f o r l a r g e r , k; b e i n g a v e c t o r of m a g n i t u d e к in t h e d i r e c t i o n of t h e incident
beam.
A p a r t i c u l a r s o l u t i o n of
( V 2 + k 2 ) ( / / ( ? ) = F (?) (11)
m a y be e x p r e s s e d in the f o r m
ф(г) = J G(?,?)F(?)d?1 (12)

IAEA - S M R - 1 2 / 4 2 473
w h e r e the G r e e n function G s a t i s f i e s
(V2 + k 2 ) G ( ? , ? ) = 6 ( r - ? ) (13)
and t a k e s the f o r m
i k
_» _» e
if 4j(r) b e h a v e s a s an outgoing s p h e r i c a l wave f o r l a r g e r . H e r e ó("ř) i s

the D i r a c delta function such that
J 6 { r - r ^ F t r ^ d ? =F(r} (15)
Hence
1 ik
ip(r) = e1i k i'- 7r .- 7 - Г eи l"r-t'l UiFMr'Jdr' (16)
_ giKj-r 47Г J r—
- ^r ' ^ U ( r )
where
TT/TA
U(?)=|^V(?) (17)
ft2
If 1? i s a v e c t o r of m a g n i t u d e к in the d i r e c t i o n of s c a t t e r i n g
k | ? - ? ' | ~ k r - l?s • (18)
a s r -» » , giving
Цв.ф) e - ^ s ' 7 ' и(Р)ф(г<)йг< (19)

4тг J
1. 3. B o r n expansion f o r s c a t t e r i n g a m p l i t u d e
B y a p r o c e s s of s u c c e s s i v e substitution we obtain the B o r n s e r i e s
= Y ^ t â (20)
n= 0
and
f(e,</>) = ^ f B n (0,<P) (21)

n= l
474 MOISEIWITSCH
where
Ф0Й = e ' V (22)
is the incident plane wave,
^nW = - 4 7 J b.pl Ufr^^frMd? (23)
and
0
W '*) = / e"^-"' u r r ' l ^ / ^ d ? (24)
T h e f i r s t B o r n a p p r o x i m a t i o n i s given by
f =
Bi " Ь J U(?)d? (25)
and
-» 1 Г ei k f r - > .7-», -»
= - i j U(r')e i' r d r ' (26)
while t h e s e c o n d B o r n a p p r o x i m a t i o n i s
f(
B2) = f
B! + f
B2 (2?)
where
F 1 Г Г -T — -» e ïbfri ] -».Г-» -» -»
B2 = ( 4 ^ J J u(rx) ~ | U ( r 2 ) e l k i " . d r , dr 2 (28)
1. 4. Phase shifts
L e t u s a s s u m e t h a t t h e p o t e n t i a l V i s s p h e r i c a l l y s y m m e t r i c a l and
d e p e n d s only on r . T h e n t h e w a v e f u n c t i o n h a s c y l i n d r i c a l s y m m e t r y about
t h e d i r e c t i o n of m o t i o n of t h e incident p a r t i c l e s c h o s e n a s p o l a r a x i s f o r
t h e c o - o r d i n a t e s г , в, <j>.
F o l l o w i n g t h e t h e o r y of F a x e n and H o l t s m a r k we expand in p a r t i a l w a v e s
00
<И?) = J^ R j f r ) P t (cosö) (29)

L =0
IAEA -SMR-12/42 475
w h e r e P{ i s a L e g e n d r e p o l y n o m i a l . Substitution into t h e S c h r ö d i n g e r
equation gives
(so.
We now s e t
1
R , ( r ) = - U | ( r ) (31)
T h i s y i e l d s t h e r a d i a l equation
{ ._ _ííí±ilj 0 (32)
dr2 + k u ( r ) U | =
w h e r e и { (0) = 0 s i n c e R £ (0) i s f i n i t e .
L e t u s s u p p o s e t h a t V(r) f a l l s off m o r e r a p i d l y than r" 2 a s r -» » .
Then
ut(r) ~ г { а { ^ ( к г ) + Ь4пг(кг)} (33)
where
=
\fžT-W< 3 ) (34)
i s a s p h e r i c a l B e s s e l f u n c t i o n , and
n { (p) = - ( - l ) ř J.i4(p) (35)
i s a s p h e r i c a l N e u m a n n f u n c t i o n , J n (p) b e i n g t h e n - t h - o r d e r B e s s e l f u n c t i o n .
Since f o r l a r g e p
sin £
jí (P) ~ ~ (P - \ *)
(36)
1 1
, - -
- cos(p
we m a y c h o o s e a { and b { so t h a t a s r -> «
u { ~ i s i n ( k r i - n + m) (37)
476 MOISEIWITSCH
where
t a n r)i = - b { / a {
Пе i s t h e p h a s e s h i f t . It v a n i s h e s when t h e p o t e n t i a l i s n u l l .
W e n o w e x p a n d t h e p l a n e w a v e in t h e f o r m
e ikz = ^ i i ( 2 £ + i) j f ( k r ) P e (cosö)
4=0
Putting
f(e) = ^ с е Р ц (cosö)
{=0
we see that f o r l a r g e r
AĚue(r) ~ i { ( 2 Í + 1) £ s i n ( k r - j i i r ) + C { e i k r
E q u a t i n g t h e c o e f f i c i e n t s of e x p ( i k r ) and e x p ( - i k r ) g i v e s
A { = i 4 ( 2 i + De'"«
С , = ^ ( 2 J > + 1) ( e 2 i " í - l )
Hence
f(e) = i У ( 2 i + 1)е'ч« s i n ^ P ^ c o s e )
1=0
and s o t h e t o t a l c r o s s - s e c t i o n i s given b y
7Г ад
Q J | ^ { 2 i + l ) e i l M s i n r^ P{ ( c o s ö ) | 2 s i n в d e
0 í=0
s i n c e du = s i n в d e d<£. Thus
со
=
Q ^ (21+1) sin? m
1=0
We note that we m a y w r i t e
Q = I m f(0)
К
IAEA - S M R - 1 2 / 1 4 477
w h i c h r e l a t e s t h e t o t a l c r o s s - s e c t i o n t o t h e i m a g i n a r y p a r t of t h e f o r w a r d
( 0 = 0 ) s c a t t e r i n g a m p l i t u d e and i s known a s t h e o p t i c a l t h e o r e m .
A n o t h e r i m p o r t a n t r e s u l t i s k n o w n a s a d i s p e r s i o n r e l a t i o n . If t h e
p o t e n t i a l p o s s e s s e s bound s t a t e s with e n e r g i e s E . , t h e r e a l p a r t of t h e
f o r w a r d s c a t t e r i n g a m p l i t u d e f o r i n c i d e n t p a r t i c l e s of e n e r g y E i s g i v e n b y
R e f ( 0 , E) = f B 1 (0, E) + ~ P / ^ / У * dE'-^R.(E) (48)
w h e r e P d e n o t e s t h e p r i n c i p a l p a r t of t h e i n t e g r a l a n d R j ( E ) i s t h e r e s i d u e
of (E 1 - E ) " x { f ( 0 , E ' ) - f B 1 ( 0 , E ' ) } a t t h e p o l e s E ' = E f . T h e i n t e g r a l m a y b e
evaluated f r o m e x p e r i m e n t a l data f o r the total c r o s s - s e c t i o n by using the
optical theorem.
T o o b t a i n a n i n t e g r a l e q u a t i o n f o r t h e p h a s e s h i f t we put
e -fk s -7' ( - i ) 1 (2Í + 1) j / k r ' ) Fe ( c o s в ' ) (49)
where
c o s ©' = c o s 0 c o s 0' + s i n Ö s i n б' сos(<t> - 0") (50)
and
CO
De'û^rMP^costf) (51)
£=0
This yields
f(0) = - ^ (2Í+ l)^4« P{(cosÖ)yV'j/krMUjtrMLKrMdr' (52)
i=о 0
so that
3 i n n s = -k J r jj(kr) Uj(r)U(r)dr (53)

о
where
us(r) ~ ^ sin(kr £ж+ r){) (54)
a s r -» <x>.
T h e f i r s t B o r n a p p r o x i m a t i o n r e p l a c e s u 8 ( r ) b y r j f ( k r ) and g i v e s
sinn{B = - k J r2{jf(kr)}2U(r)dr (55)

о
478 MOISEIWITSCH
We can a l s o choose the a l t e r n a t i v e a s y m p t o t i c f o r m f o r l a r g e r
u { ( r ) ~~ s i n ( k r £ir) + t a n r]{ c o s ( k r lit) (56)
in w h i c h c a s e t h e i n t e g r a l e q u a t i o n f o r t h e p h a s e s h i f t b e c o m e s
t a n r]{ = - J r j£(kr)u£(r)U(r) d r (57)

0
a n d t h e f i r s t B o r n a p p r o x i m a t i o n i s now
tann№ =-kj r 2 {j { (kr)} 2 U(r) d r (58)

о
If t h e p o t e n t i a l V ( r ) f a l l s off e x p o n e n t i a l l y a s r -» <», we h a v e t h e
effective-range expansion
k2t+1cot m = - —
a
+ I % k 2 + 0(k 4 ) (59)
i *
Suppose ař is finite. Then nir a s к -» 0.

L e v i n s o n ' s t h e o r e m s t a t e s t h a t n i s t h e n u m b e r of b o u n d s t a t e s with t h e
a n g u l a r m o m e n t u m <J£{i + 1) ti p o s s e s s e d b y t h e p o t e n t i a l V ( r ) .
Now s u p p o s e a"/ = 0 s o t h a t а.ц i s i n f i n i t e . T h e n -» (n+f)7r a s к -» 0
a n d t h e r e i s a n a d d i t i o n a l s t a t e of z e r o e n e r g y .
C o n s i d e r t h e £ = 0 o r s - w a v e and l e t
a = - l i m ^ t a n rj0 (60)
к-* о k
T h i s is called the s c a t t e r i n g length; the total c r o s s - s e c t i o n at z e r o incident-

p a r t i c l e e n e r g y i s given by
Q(0) = 4тга2 (61)
since ^ sin 0 a s к -» 0 f o r i ž 1.
1.5. Scattering m a t r i x
Taking
u t ( k , r ) ~ А,(к) s i n { k r -\SLi + n £ (k)} (62)
w e c a n c h o o s e A { (k) s o t h a t f o r l a r g e r
u t ( k , r ) ~ e" iltr - е ш
St(k)eikr (63)
IAEA - S M R - 1 2 / 1 4 479
where
S^k) = e2iic(k) (64)
T h e SjjCk) a r e the d i a g o n a l e l e m e n t s of a m a t r i x c a l l e d the s c a t t e r i n g

m a t r i x S. In t h e p r e s e n t c a s e t h e o f f - d i a g o n a l e l e m e n t s of S v a n i s h s i n c e
t h e a n g u l a r m o m e n t u m d o e s not c h a n g e and t h e r e i s a s i n g l e c h a n n e l only.
T h e d i a g o n a l e l e m e n t S { (k) of t h e S - m a t r i x s a t i s f i e s
S t (k) = S j V k ) , S<,(k) = S { (-k) (65)
and t h u s
S"1 (k) = S { (-k) = § t (k) (66)
so that S is unitary:
SS* = I_ (67)
Bound s t a t e s will o c c u r f o r t h o s e v a l u e s of к w h e r e S^k) h a s a pole

so that f o r large r
Uj (к, r) ~ e i k r (68)
F o r к = i« , w h e r e к. i s r e a l and p o s i t i v e ,
^ -кг (69)
щ ~~ e
which t h e r e f o r e c o r r e s p o n d s t o a bound s t a t e .
If Sj(k) h a s a pole at a point k , then it a l s o h a s a pole at -k and z e r o s
at -K and K. T h u s , c o r r e s p o n d i n g to the pole a t К = ÍK, t h e r e i s a z e r o of
S s (k) at к = -i/c.
It i s a l s o u s e f u l to c h o o s e t h e a s y m p t o t i c f o r m
us(r) - sin(kr4í7r) + K £ c o s ( k r - i í 7 r ) (70)
where
Kj = tan m (7D
a r e t h e d i a g o n a l e l e m e n t s of t h e K - m a t r i x . We s e e that
The partial cross-section can be conveniently e x p r e s s e d in t e r m s of

t h e d i a g o n a l e l e m e n t T{ of t h e T m a t r i x d e f i n e d by
T =S - I (73)
480 MOISEIWITSCH
s o that
T _2iKL
1 -iK
2i t a n rje
, •+ (74)
1 - i t a n oi
We h a v e
sin2
Q{ = £2 + ne
= p ( 2 f + 1) | T J 2 (75)
1.6. Inelastic collisions
U s i n g e x p r e s s i o n (4) f o r t h e c u r r e n t d e n s i t y J^ t h e net i n w a r d r a d i a l
flux of e l a s t i c a l l y s c a t t e r e d p a r t i c l e s i s
Now f o r l a r g e r we h a v e
CO
p ~ У {(2SL+ 1)1® (kr)" 1 s i n ( k r - i i ? r ) + е' кг }Р £ (cos tf) (77)

í=0
where
C j = (2ik) _ 1 (2í + l) (e 2i "í - 1) (78)
and h e n c e
с 1 + ё с (79)
Ч = - Ш й т т 1 ' > < - '
{=0
If r^ i s r e a l t h e e x p r e s s i o n v a n i s h e s . Suppose now that ns i s c o m p l e x .
We put ne = a t + iße w h e r e a t and ßj, a r e r e a l . T h e n
C{ { sin 2 » , e _2s t + i (1-со8 2^е"281! )} (80)
and so
00
F =
i 2^k I (2i+l)(l-e«i) (81)
i= 0
IAEA - S M R - 1 2 / 1 4 481
Now c o n s i d e r i n e l a s t i c a l l y s c a t t e r e d p a r t i c l e s with f i n a l s p e e d v n
and wave n u m b e r k n = m v n / h . If the c o r r e s p o n d i n g i n e l a s t i c a l l y s c a t t e r e d
s p h e r i c a l wave i s given at l a r g e d i s t a n c e s by
f„ (ö) ^ e ik n r (82)
the r a d i a l flux d e n s i t y of i n e l a s t i c a l l y s c a t t e r e d p a r t i c l e s i s
vn|fn(e)|2/r2 (83)
and the i n e l a s t i c c r o s s - s e c t i o n i s given b y
(Q i n ) n = y / | f n ( 6 ) | 2 s i n e d0 d<*> (84)
T h e r e f o r e the o u t w a r d flux of i n e l a s t i c a l l y s c a t t e r e d p a r t i c l e s with wave

n u m b e r kn i s
•fík
~ (Qin)n (85)
Now the i n w a r d flux of e l a s t i c a l l y s c a t t e r e d p a r t i c l e s i s e q u a l t o t h e outward

f l u x of a l l i n e l a s t i c a l l y s c a t t e r e d p a r t i c l e s . H e n c e t h e t o t a l i n e l a s t i c c r o s s -
s e c t i o n i s given by
Qin =X ( Q in»n I Ш e 40{)

" (86
>
n É=0
C l e a r l y Q i n v a n i s h e s if ße = 0, i. e. if ne i s r e a l . F u r t h e r , the elastic c r o s s -
s e c t i o n i s given by
Q
e« 2 i + 1 I0«'
i=0
= | f J " (2Í +l)e" z ß i(cosh2/3 { - c o s 2 ö i ) (87)

4=0
F o r a d e t a i l e d d i s c u s s i o n of s c a t t e r i n g t h e o r y t h e r e a d e r should
c o n s u l t Mott and M a s s e y (The T h e o r y of A t o m i c C o l l i s i o n s , O x f o r d (1965)).
and, f o r e x a m p l e , Schiff (Quantum M e c h a n i c s , M c G r a w - H i l l (1968)) o r
R o d b e r g and T h a l e r ( I n t r o d u c t i o n to t h e Q u a n t u m T h e o r y of S c a t t e r i n g ,
A c a d e m i c P r e s s (1967)).
482 MOISEIWITSCH
2. VARIATIONAL M E T H O D S
2.1. Hulthén's variational principle
We i n t r o d u c e the d i f f e r e n t i a l o p e r a t o r L given by
t - d^ i i 2 tr / \ W+\) /. \
~ dr 2 " ~Ufr) за (1)
s o t h a t the r a d i a l equation m a y b e w r i t t e n
Lu = 0 (2)
d r o p p i n g the s u b s c r i p t I . Now defining the f u n c t i o n a l

OO
I[v] =Jv L v dr (3)

0
w h e r e v i s an a r b i t r a r y q u a d r a t i c a l l y i n t e g r a b l e f u n c t i o n of r , we s e e that
I[u] = 0 (4)
w h e r e u(0) = 0 and f o r l a r g e r
u ~ ^ sin ( k r -1* H i t + n) (5)

К ů
Next c o n s i d e r t h e f u n c t i o n u + 6u d i f f e r i n g i n f i n i t e s i m a l l y f r o m u,
v a n i s h i n g at r = 0 , and h a v i n g the a s y m p t o t i c f o r m f o r l a r g e r
u + óu ~ ^ s i n ( k r - ^-SLtt + ц + 6ri) (6)

К tL
L e t 6I[u] denote t h e c o r r e s p o n d i n g s m a l l change in I[u], Then
6I[u] = J 6 u L u d r + J u L6u d r + J 6u Lóu d r (7)

О О О
and s i n c e
Г d2u . Г d t du
u 6 u d r =-J 66u ^ dd rr ++ Г[ ud r-
uZP" u u6U-6U
uu
d ? J - dr
0
(8)
d2 1
* u л x
óu r;—5* dr - г öl
dr2 k
IAEA -SMR-12/14 483
it follows that
6I[u] = 2 I 6u L u d r - ^ 0Г1 (9)
n e g l e c t i n g q u a n t i t i e s of the second o r d e r of s m a l l n e s s . But Lu = 0 and

thus
ól[u] = - f ón (10)
к
which is known a s H u l t h é n ' s v a r i a t i o n a l p r i n c i p l e .
2. 2. H u l t h é n ' s and K o h n ' s v a r i a t i o n a l m e t h o d s
We choose v a r i a t i o n s of u f o r which 6I[u] = 0. Then I r e m a i n s z e r o and

Ón = 0. T h i s s t a t i o n a r y p r o p e r t y of n m a y be u s e d to find an a p p r o x i m a t e
value f o r n and an a p p r o x i m a t e r a d i a l function u(r) a s d e s c r i b e d in the
following.
We t a k e a t r i a l function u t ( r ) , s a t i s f y i n g u t (0) = 0 and f o r l a r g e r
u t ( r ) ~ £ s i n ( k r S t i r + rit) (11)
depending on n p a r a m e t e r s c ; (i = 1, . . . , n) and the p h a s e shift p a r a m e t e r

r)t. The function u t ( r ) i s then substituted f o r v in I[v] and the n + 1
p a r a m e t e r s d e t e r m i n e d f r o m the n + 1 equations
I t = 0, =0 (i = 1, . . .n) (12)
9c j
w h e r e I t = I[u t ], the p h a s e shift being a p p r o x i m a t e d by n t . T h i s is known

a s Hulthén's variational method.
An a l t e r n a t i v e and u s u a l l y s u p e r i o r p r o c e d u r e depends on the s t a t i o n a r y
p r o p e r t y of I + (l/k)r). In t h i s m e t h o d the p a r a m e t e r s Cj and rjt a r e d e t e r -
m i n e d by
9I t = _ 1_ _8I
kk - 0 (i = 1 , . . . , n) (13)
ant ' Tc{
the p h a s e shift now being given by
1v = < ? t + k l t (14)
s i n c e I t d o e s not n e c e s s a r i l y v a n i s h . T h i s i s called K o h n ' s v a r i a t i o n a l

method.
484 MOISEIWITSCH
If u(r) h a s the a s y m p t o t i c f o r m f o r l a r g e r
u ( r ) ~ sin ( k r - £ir) + a cos (kr - ^ lir) (15)
w h e r e в = t a n n, H u l t h e n ' s v a r i a t i o n a l p r i n c i p l e b e c o m e s
ól[u] = - к б о (16)
Suppose u t ( r ) i s a t r i a l f u n c t i o n s a t i s f y i n g u t (0) = 0 and f o r l a r g e r
ut(r) ~ sin(kr HIT) + a t c o s ( k r - ^ in) (17)

i! Ů
Then Kohn's variational method u s e s the equations
ib.=0 (1 = 1 , . . . . n) (18)
da t dC;
t o d e t e r m i n e t h e p a r a m e t e r s a t and Cj. T h e p h a s e s h i f t i s now

a p p r o x i m a t e d by r)v w h e r e
tan n v = = at + £ It (19)
2. 3. Schwinger's variational principle
T h e v a r i a t i o n a l p r i n c i p l e f o r the p h a s e s h i f t due to Schwinger p r o v i d e s

a s t a t i o n a r y e x p r e s s i o n f o r к cot q.
We i n t r o d u c e the G r e e n f u n c t i o n
G(r,r') = -кГ<к. ^ ( k r j n j k r j (20)
w h e r e r<( a r e the l e s s e r and g r e a t e r of r , r ' , which s a t i s f i e s
+ k2 - ^ ^ f 1 1
} G(r, r') = -б(г-г') (21)
C h o o s i n g u(r) t o h a v e t h e a s y m p t o t i c b e h a v i o u r f o r l a r g e r
u ( r ) ~ k r { j j i k r ) - t a n ц n { (kr)} (22)
we m a y w r i t e
u ( r ) = k r jj(kr) - J G i r . r M U f r ' j u i r M d r ' (23)

о
IAEA - S M R - 1 2 / 1 4 485
so that
tanrj = - J r'jifkr'lUfr'Jufr'Jdr' (24)

о
M u l t i p l y i n g both s i d e s of t h e i n t e g r a l e q u a t i o n (23) by U ( r ) u ( r ) and

integrating over r yields
J k r j{(kr)U(r)u(r)dr (25)
0
= J U(r){u(r)} 2 dr +J u ( r ) U ( r ) d r J G ( r , r ' i U i r ' J u f r ' J d r 1

so il.
t h a t4. 0 O r ",
к cot rj
(26)
J U(r){u(r)} d r + / u ( r ) U ( r ) d r fG(r, r'JUir'Mr'Jdr1
0 0 0
if r j £ ( k r ) U ( r ) u ( r ) d r } 2
0
w h i c h i s t h e e x p r e s s i o n f o r к cot n deduced b y S c h w i n g e r .
We now s i m p l i f y o u r n o t a t i o n be defining
(g.nf) = J gQfdr (27)

о
where Q is a differential or integral operator. Then
(u, Uu) + (u, UKu) , ,

k COt = L (28
- (u, Uf) '
where К denotes the integral o p e r a t o r
К = J dr'G(r, r')U(r') (29)

and °
f(r) - r j g ( k r ) (30)
Now d e f i n i n g the r e a l H e r m i t i a n o p e r a t o r
n = - U ( l + K) (31)
and i n t r o d u c i n g t h e f u n c t i o n a l
486 MOISEI W I T S C H
we obtain
к cot n = J[u] (33)
w h e r e u s a t i s f i e s t h e i n t e g r a l equation
u = kf - Ku (34)
i. e.
fžu = -kUf (35)
Since J[v] i s a h o m o g e n e o u s f u n c t i o n of v we m a y n o r m a l i z e by taking

(v, Uf) = 1. T h e n
J[v] = (v, Qv) (36)
a n d , with the s a m e n o r m a l i z a t i o n , u s a t i s f i e s
Пи = ajUÍ (37)
where
и = (u, fiu) = к cot n (38)
Now s u p p o s e that 6J[v) i s t h e c h a n g e in J[v] r e s u l t i n g f r o m an

i n f i n i t e s i m a l v a r i a t i o n öv. Since v i s r e a l and fi i s a H e r m i t i a n o p e r a t o r ,
we s e e t h a t
fij[v] =2(6v, fiv) + (óv, Í26v) (39)
F u r t h e r , b e c a u s e of the n o r m a l i z a t i o n condition, we h a v e
( óv, Uf) = 0 (40)
It f o l l o w s t h a t to t h e f i r s t o r d e r of s m a l l q u a n t i t i e s
6J[u] = 0 (41)
which e s t a b l i s h e s t h e s t a t i o n a r y p r o p e r t y of the S c h w i n g e r f u n c t i o n a l .
A s a s i m p l e e x a m p l e we t a k e the t r i a l f u n c t i o n
u t ( r ) = k r jj(kr) (42)
IAEA - S M R - 1 2 / 1 4 487
c o r r e s p o n d i n g to t h e u n p e r t u r b e d incident w a v e . T h e n s u b s t i t u t i n g u t
f o r v in t h e S c h w i n g e r f u n c t i o n a l we obtain the a p p r o x i m a t i o n
{k J r 2 [ j i ( k r ) ] 2 U ( r ) d r } 2
t a n ns = - —й « S
к ! r 2 ^,, (kr)} 2 U(r)dr + к I r j„ ( k r ) U ( r ) d r f G ( r , r ' ) U ( r ' ) r ' j „ ( k r ' ) d r '
0 0 " 0 *
(43)
_ (tan n B i) 2
t a n r/B1 - t a n n B2
We note t h a t if t h e s e c o n d B o r n t e r m tan r,B2 i s s m a l l c o m p a r e d to t h e f i r s t

B o r n t e r m t a n r)B1 then
ten r)s - tanr7 B 1 + t a n n B 2 (44)
which i s j u s t t h e second B o r n a p p r o x i m a t i o n to t a n n. T h u s t a n ns i s a l s o
t h e f i r s t P a d é a p p r o x i m a n t given by
t a n OBI
IB1
t a n rjp = (45)
1 -к
w h e r e к = t a n rj B 2 /tan rjBi i s c h o s e n s o a s t o yield t h e second B o r n

a p p r o x i m a t i o n on expanding the d e n o m i n a t o r .
2. 4. S c h w i n g e r bounds to the p h a s e shift
We u s e t h e m o n o t o n i c i t y t h e o r e m that if two p o t e n t i a l s ( l o c a l o r n o n -
local) Va and Vb s a t i s f y
ě
(Ф, \Ф) (Ф, \Ф) (46)
f o r a l l f u n c t i o n s ф, t h e n t h e c o r r e s p o n d i n g p h a s e s h i f t s rja and Пь s a t i s f y
% § 1b (47)
Suppose t h a t V(r) ě 0 f o r a l l r . T h e n by S c h w a r t z ' s i n e q u a l i t y
(ф,Уф) š (ф, У5ф) (48)
where
s o t h a t Vs i s t h e i n t e g r a l o p e r a t o r
V(r)v(r) Г d r ' v ( r ' ) V ( r ' )

V (50
s= >
and v(r) i s an a r b i t r a r y f u n c t i o n . H e n c e we h a v e
n s ns (51)
w h e r e ns i s t h e p h a s e s h i f t c o r r e s p o n d i n g to t h e n o n - l o c a l p o t e n t i a l Vs .
Now it can be shown t h a t
к cot n s = J[v] (52)
which i s j u s t the a p p r o x i m a t i o n t o к cot n given by t h e S c h w i n g e r v a r i a t i o n a l

principle.
Consequently, if V(r) ž 0 f o r all r ( r e p u l s i v e potential), t h e S c h w i n g e r
p h a s e s h i f t rjs p r o v i d e s an u p p e r bound t o t h e e x a c t p h a s e s h i f t ц.
A l t e r n a t i v e l y , if V(r) s 0 f o r all r ( a t t r a c t i v e potential), t h e S c h w i n g e r
p h a s e s h i f t rj s i s a l o w e r bound t o r).
2.5. U p p e r bound t o s c a t t e r i n g length
In the p r e s e n t s e c t i o n we d e s c r i b e t h e t h e o r y o r i g i n a t e d by Spruch and

R o s e n b e r g ( P h y s . Rev. HJ3 (1959) 1034). T h e s c a t t e r i n g of p a r t i c l e s
h a v i n g v a n i s h i n g e n e r g y and z e r o a n g u l a r m o m e n t u m is r e p r e s e n t e d by the
solution of t h e r a d i a l equation
Lu = 0 (53)
where
L = - U(r) (54)
and
u(r) ~ a - r (55)
f o r l a r g e r, the s c a t t e r i n g length being denoted by a.

We i n t r o d u c e a t r i a l f u n c t i o n u t ( r ) s a t i s f y i n g u t (0) = 0 and f o r l a r g e r
ut(r) ~ a t - r (56)
Defining
w(r) = u t ( r ) - u ( r ) (57)
IAEA - S M R - 1 2 / 1 4 489
we obtain
u t L u t d r = j wLw d r + j u L w d r = j w L w d r + | u r j ^ - w ^ (58)
giving
a = at - J u t Lu t d r + J wLwdr (59)
о о
If t h e p o t e n t i a l V(r) h a s no bound s t a t e s t h e n
Х Ш dT s 0 (60)
where
H =- V 2 + V(r) (61)
2m
and x i s a q u a d r a t i c a l l y i n t e g r a b l e f u n c t i o n , i . e . / x 2 dT < со. Hence, setting
x(r) = r _ 1 w ( r , A.) (62)
w h e r e w(r,X) = w(r)exp(-Xr), we s e e t h a t
K(A.) = / w ( r , X ) L w ( r , X ) d r š 0 (63)
s i n c e w(r,A) i s q u a d r a t i c a l l y i n t e g r a b l e although w(r) i s not. B u t it can

b e shown t h a t K(A) i s continuous at X = 0 and so
w(r) Lw(r) d r s 0 (64)
It f o l l o w s t h a t
a s at - / u t L u t d r (65)
a r e s u l t f i r s t e s t a b l i s h e d by S p r u c h and R o s e n b e r g .
F o r t h e z e r o - e n e r g y c a s e , H u l t h é n ' s v a r i a t i o n a l p r i n c i p l e t a k e s the
form
6I[u] = 6a (66)
and t h e Kohn e q u a t i o n s a r e
9I t , 3L
^ = 1. ^ =0 (i=l,...n) (67)
Now we s u p p o s e that t h e r e e x i s t s a single bound s t a t e f o r t h e p o t e n t i a l

V ( r ) . We e m p l o y the t r i a l f u n c t i o n
Ut'(r) = u t ( r ) + d l U l t ( r ) (68)
w h e r e r " 4 i l t ( r ) i s a f u n c t i o n r e p r e s e n t i n g the bound s t a t e . We h a v e
av = at - u{ Lu; d r
(69)
a t - / u t Lu t d r - 2dj^ / u l t L u t d r - d j
where
OO
e = U
it f ltLUltdr i70)
0
s o that E l t = ( - f i 2 / 2 m ) e l t p r o v i d e s an u p p e r bound t o t h e e n e r g y of t h e
bound s t a t e . On s e l e c t i n g t h e o p t i m u m value of d j obtained by u s i n g
9I[uj] . .
— — = 0 which g i v e s
OQ j
CO
dl = - ~ / ultLutdr (71)
о
we a r r i v e at t h e r e s u l t
OO
+ u
utLutdr ^ f i t Lu, d r j (72)
It c a n be p r o v e d t h a t a v š a and t h u s we have obtained an u p p e r bound to

t h e e x a c t s c a t t e r i n g length in t h i s c a s e a l s o .
T h i s r e s u l t c a n be g e n e r a l i z e d to c a s e s in which t h e r e e x i s t m o r e
t h a n o n e bound s t a t e .
A d e t a i l e d a n a l y s i s of v a r i a t i o n a l m e t h o d s c a n b e found in t h e a r t i c l e
by S p r u c h ( L e c t u r e s in T h e o r e t i c a l P h y s i c s , Vol.4, B r i t t i n et a l . , E d s ,
I n t e r s c i e n c e P u b l . (1962)) 218 and M o i s e i w i t s c h ( V a r i a t i o n a l P r i n c i p l e s ,
I n t e r s c i e n c e P u b l . (1966)).
IAEA - S M R - 1 2 / 1 4 491
3. E L A S T I C SCATTERING O F E L E C T R O N S BY ATOMS
3.1. H y d r o g e n a t o m s
The S c h r ö d i n g e r e q u a t i o n f o r t h e s y s t e m of i n c i d e n t e l e c t r o n and
h y d r o g e n atom is
(H-E) Ф = 0 (1)
w h e r e E is t h e t o t a l e n e r g y and
is the total Hamiltonian.

If we w r i t e the t o t a l wave f u n c t i o n in t h e s e p a r a b l e f o r m
=F i î j ) ^ ) (3)
w h e r e ф 1 is t h e ground s t a t e wave f u n c t i o n of a t o m i c h y d r o g e n with t h e

eigenenergy E j satisfying
v 2
- i £ -т-)мг> = ЗДг) (4)
we obtain
Vii 2 + k 2 ŤT V ^ r j l j F ( ? j ) = 0 (5)
where
V ^ i ) =/ {^(r2)}2 + (6)
i s t h e s t a t i c p o t e n t i a l of a t o m i c h y d r o g e n and
+ (7)
к b e i n g the wave n u m b e r of the i n c i d e n t e l e c t r o n and a 0 b e i n g the B o h r r a d i u s .
A p a r t i a l - w a v e e x p a n s i o n l e a d s to the d i f f e r e n t i a l e q u a t i o n
{ ^ - U i M - ^ j v r H o
where
If we e x p r e s s r in t e r m s of a 0 and e n e r g y in t e r m s of e 2 / 2 a 0 ( R y d b e r g )
s o t h a t к is e x p r e s s e d in t e r m s of aj 1 , then
2 r
иг(г) = - 2 ( i + l ) e ' (10)
C o n s i d e r t h e SL = 0 p a r t i a l wave. T h e e q u a t i o n c a n be r e a d i l y s o l v e d
e x a c t l y by n u m e r i c a l m e t h o d s . But a c c u r a t e r e s u l t s c a n a l s o b e o b t a i n e d
u s i n g Kohn' s v a r i a t i o n a l m e t h o d with t h e e x t r e m e l y s i m p l e t r i a l f u n c t i o n
U t (r) = s i n k r + a t (1 - e"*11) c o s k r
По
к numerical variational
0 -9.44* -9.445*
0.2 0.97252 0.97249
0.4 1.05749 1.05747
0.6 1.02103 1.02101
0.8 0.96336 0.96332
1.0 0.90552 0.90547
Scattering length
Since t h e s t a t i c p o t e n t i a l h a s no bound s t a t e it follows f r o m L e v i n s o n 1 s

t h e o r e m that ч0->0 a s k - * 0 .
T h e above a n a l y s i s h a s a s s u m e d t h a t the h y d r o g e n atom is u n a f f e c t e d
by t h e p r e s e n c e of t h e i n c i d e n t e l e c t r o n . Actually t h e e l e c t r i c f i e l d of t h e
e l e c t r o n p o l a r i z e s t h e atom and t h i s p r o d u c e s a l o n g - r a n g e p o t e n t i a l which
for large r behaves like
i ГУ P2
V(r) ~ 2-SL*- (12)
r
w h e r e a is t h e dipole p o l a r i z a b i l i t y of t h e a t o m which, f o r t h e c a s e of
h y d r o g e n , h a s t h e v a l u e a = (9/2) ag. T h e e f f e c t i v e - r a n g e f o r m u l a d e r i v e d
b y B l a t t and J a c k s o n ( P h y s . R e v . 76_ (1949) 18) and B e t h e ( P h y s . Rev. 76
(1949) 38) f o r s h o r t - r a n g e p o t e n t i a l s is then no l o n g e r a p p l i c a b l e and m u s t
b e r e p l a c e d by the e x p a n s i o n d e r i v e d by O' M a l l e y , S p r u c h and R o s e n b e r g
(J. M a t h . P h y s . 2 (1961) 491) which f o r SL = 0 i s
ira 2
к cot r)o = " ~ + Tě? k + f k
da
ln^-
lb
+0(k 2) (13)
IAEA - S M R - 1 2 / 1 4 493
and f o r Í > 0 is
к 2 cot rjp = e
—( i + f ) ( i + è ) ( / - i— + higher-order terms. (14)
7та
So f a r we have n e g l e c t e d t h e P a u l i e x c l u s i o n p r i n c i p l e . To t a k e it into
a c c o u n t we s y m m e t r i z e t h e s p a t i a l wave f u n c t i o n f o r t h e whole s y s t e m by
writing
Ф ^ Д ) { F^rîrz) ± F± (г^Ф^)} (15)
w h e r e the + s i g n c o r r e s p o n d s to s i n g l e t s c a t t e r i n g and t h e - sign to t r i p l e t

s c a t t e r i n g . T h i s allows f o r e l e c t r o n e x c h a n g e .
S u b s t i t u t i n g into t h e S c h r ö d i n g e r equation f o r t h e t o t a l s y s t e m y i e l d s
an e q u a t i o n of the f o r m
{V2 + k 2 - U 1 ( r 1 ) } F ± ( ï 1 ) ± J K( ï j , r 2 ) F ± ( r 2 ) dr 2 = 0 (16)
Now m a k i n g an e x p a n s i o n in p a r t i a l wave y i e l d s
00
с 2 ""i
+ k 2
j j ^ "ui ( r )
-^7T^}u£(r)±JT<cí(r,r')uí±(r')dr' =0 (17)
0
where
Kt(r,r') = 2JTX r r ' ^ ( r ) ^ ( r ' ) { ^ ( Е - г Е ^ б м - ^ ^ г . г ' ) } (18)
and
7t(r,r') = r Í / г ^ 1 (19)
Using the s a m e simple t r i a l function as f o r the central-potential c a s e

t o g e t h e r with Kohn' s v a r i a t i o n a l m e t h o d gives t h e following v a l u e s f o r t h e
phase shifts:
1o "o
к numerical variational numerical variational
0 2.350* 2.350* 8.095* 8.297*
0.2 2.679 2.679 1.871 1.853
0.4 2.257 2.257 1.239 1.315
0.6 1.901 1.900 0.869 1.048
0.8 1.614 1.614 0.651 0.954
1.0 1.391 1.390 0.543 0.831
* Scattering length
Ask-» 0 we h a v e nö and i j -*• т . T h i s is in a c c o r d a n c e with t h e g e n e r a l i z a t i o n

of L e v i n s o n 1 s t h e o r e m d i s c u s s e d by Swan ( P r o c . R. Soc. (London) A228
(1955) 10).
A m o r e a c c u r a t e a p p r o a c h is the p o l a r i z e d - o r b i t a l m e t h o d of T e m k i n
( T e m k i n , L a m k i n , P h y s . Rev. 121 (1961) 788) which involves t h e u s e of a
t r i a l f u n c t i o n having t h e f o r m
=3= [ F ^ K ^ ) + Фро1(гг,г2)} ±¥±(г2){ф1(г1)+фро1(г2,г1)}]

(20)
w h e r e фро} allows f o r dipole p o l a r i z a t i o n and is given by
^poÄ.R,) = - e f r ^ r ^ i r , ; , ) ф- r | + r 2 ^) c o s 0 1 2 (21)
with
«<•»••*>• {S ï 5 Ï Î
T h i s f u n c t i o n l e a d s to the dipole p o l a r i z a t i o n p o t e n t i a l
Vpoi(r) = (23)
where
e(r) = f { l - ( l + 2 r + 2 r 2 + | r 3 + | r 4
+ 1 i r5)e"2tj (24)
in a t o m i c u n i t s . T h e f i r s t f i v e t e r m s in t h e p a r e n t h e s e s a r e c o m p l e t e l y
d e t e r m i n e d b y t h e r e q u i r e m e n t that Vpoi ~ r f o r s m a l l r .
T h e m o s t a c c u r a t e c a l c u l a t i o n s w e r e p e r f o r m e d by S c h w a r t z ( P h y s .
Rev. 124 (1961) 1468) who u s e d an e l a b o r a t e t r i a l f u n c t i o n of t h e f o r m
= (25)
71 (Flr^.r 12 )Ф 1 (г 2 ) ± F*(rs
where
F i r j . r j . r j j ) = r ^ í s i n k r-[ + a t ( 1 - e " № ) c o s k r a }
(26)
х 11 11
+
+
\ n <=."(№ + r 'г) rJ" -r
/ 4mne 12 r r
2
C, m, n
and obtained t h e u p p e r bounds to the s c a t t e r i n g l e n g t h s
a + = 5.965 a 0 a . = 1.769 a Q
C a l c u l a t i o n s a l o n g a n a l o g o u s l i n e s have a l s o b e e n p e r f o r m e d on t h e
e l a s t i c s c a t t e r i n g of p o s i t r o n s by h y d r o g e n a t o m s . F o r s c a t t e r i n g by t h e
IAEA - S M R - 1 2 / 1 4 495
s t a t i c p o t e n t i a l of a t o m i c h y d r o g e n a = 0.582 a 0 i s o b t a i n e d , t h e p o s i t i v e
s i g n i n d i c a t i n g t h e r e p u l s i v e n a t u r e of t h i s p o t e n t i a l . S c h w a r t z ' s c a l c u l a t i o n ,
h o w e v e r , y i e l d s a = - 2 . 1 0 a0, t h e n e g a t i v e s i g n s h o w i n g t h a t p o l a r i z a t i o n
of t h e a t o m y i e l d s a n o v e r a l l a t t r a c t i v e p o t e n t i a l b e t w e e n t h e p o s i t r o n and
the atomic hydrogen s y s t e m . A p o l a r i z e d - o r b i t a l calculation (Allison,
M c l n t y r e , M o i s e i w i t s c h , ( P r o c . P h y s . Soc. 7J3 (1961) 1169) y i e l d s a = - 0 . 7 9 aQ
and l e a d s to the s a m e c o n c l u s i o n .
3.2. F i r s t and s e c o n d B o r n a p p r o x i m a t i o n s
An a l t e r n a t i v e w a y of a l l o w i n g f o r p o l a r i z a t i o n i s to i n c l u d e c o u p l i n g
to e x c i t e d s t a t e s b y e x p a n d i n g t h e t o t a l w a v e f u n c t i o n in t e r m s of t h e e i g e n -
s t a t e s of a t o m i c h y d r o g e n . N e g l e c t i n g e x c h a n g e w e m a y s e t
Ф (?! ,? 2 ) = S F m ( ? j )фт(гг ) (27 )

m
w h e r e фт is t h e e i g e n f u n c t i o n w i t h e i g e n e n e r g y E m s a t i s f y i n g
2
V - — V (r) = E é ( r ) (28)
V 2m r /'»' '
On s u b s t i t u t i n g into t h e S c h r ö d i n g e r e q u a t i o n f o r t h e w h o l e s y s t e m we find
(V2 + k 2 ) F „ ) = S и п г Д )F m (?! ) (29)
where
•h 2 k 2
E„ = E (30)
2m
and
U - A -ï-^фm{r2)dr2 (31)
If t h e h y d r o g e n a t o m i s i n i t i a l l y in t h e g r o u n d s t a t e (n = 1) and t h e
i n c i d e n t b e a m of e l e c t r o n s h a s a w a v e v e c t o r k x we h a v e f o r l a r g e r
Fl (r) ~ e ^ i ' " + ^ e i k i r f i ( M ) (32)
F n (r) ~±е 1 к п'^(е,ф) (n/1) (33)
so that
1
= e^' + rG1(r,r1)Sulm(ï1)Fm(?1)d?1 (34)
F n (?) = f G^r.r,) S U n m (? 1 )F m (? 1 ) d ^ (35)

^ m
w h e r e t h e G r e e n f u n c t i o n i s given by
1
r i ^ i - - exp(ikn|r-ri|)
Ir-rJ
This yields
f n (6) = SjT e - ' V n u ^ F j ^ ) ^ (37)
—>
w h e r e k n i s t h e wave v e c t o r of the s c a t t e r e d p a r t i c l e and s u b t e n d s t h e

s c a t t e r i n g angle 0 to t h e d i r e c t i o n k j of the incident b e a m .
T h e f i r s t B o r n a p p r o x i m a t i o n i s o b t a i n e d by s e t t i n g
F1(r) = eiî'" (38)
Fm(?)=0 ( m f 1) (39)
and gives
f 1)(0 =
í > "ér Unťr^d?! (40)
w h e r e k s i s t h e wave v e c t o r of an e l a s t i c a l l y s c a t t e r e d p a r t i c l e . Putting
К = к i - k s we find
f<4(K) = (41)
where К = | k | = 2 kjsiníe/ž).
If К » 1 we h a v e f ^ ~ 2 / K 2 so t h a t
- 2k2 sin2(6/2) (42)
and t h e r e f o r e t h e d i f f e r e n t i a l e l a s t i c c r o s s - s e c t i o n i s given by
1(0) = l f > ) | ' ~ 4 k t B ^( 0 / 2 ) («)

IAEA - S M R - 1 2 / 1 4 497
w h i c h i s i d e n t i c a l with t h a t f o r t h e e l a s t i c s c a t t e r i n g of e l e c t r o n s by t h e
C o u l o m b field of a p r o t o n ; so at high e n e r g i e s the e f f e c t of t h e s c r e e n i n g
f r o m t h e a t o m i c e l e c t r o n is negligible e x c e p t at v e r y s m a l l a n g l e s of
scattering.
T h e s e c o n d B o r n a p p r o x i m a t i o n is obtained by s e t t i n g
Fj(r) = eikl'1 + / G1(r,r1)Un(r1)eikl'ri d r j (44)
Fm(r) = Gm(r,ri)Vml(ri)e^h dïj (45)
so that
f(2)=fBi + f
B2 (46)
w h e r e f B 1 = f ( 1 ) is t h e f i r s t B o r n a p p r o x i m a t i o n and
U
^ " - - b š f f ^ i m ( r i ) G m ( ? i , ? 2 ) U m l ( ? 2 ) e r k ' ^ <Ц d r 2 (47)
is t h e s e c o n d B o r n c o r r e c t i o n t e r m .
I n t r o d u c i n g t h e q u a n t i t i e s a = Re (f B 2 /f B 1 ) and ß = Im (f B 2 /f B 1 ) we s e e t h a t
1(0) = |f B 1 + f B 2 | 2
(48)
|fB1|2{(l+a)2 +ß2}
H o w e v e r , a t e r m of the f o u r t h o r d e r in t h e i n t e r a c t i o n e n e r g y b e t w e e n
t h e i n c i d e n t e l e c t r o n and t h e h y d r o g e n a t o m h a s b e e n n e g l e c t e d . T h u s
defining a 1 = R e f f g g / ^ j ) w h e r e f B3 is t h e t h i r d B o r n - a p p r o x i m a t i o n c o r r e c t i o n
to t h e s c a t t e r i n g a m p l i t u d e , we find t h a t to t h e f o u r t h o r d e r
1(0) = | f B 1 | 2 {(1 +a)2 + 2a< +ß2} (49)
Since a ' is n e g l e c t e d above, to be c o n s i s t e n t it is n e c e s s a r y to i g n o r e all

t e r m s of t h e f o u r t h o r d e r giving the t h i r d - o r d e r a p p r o x i m a t i o n
1(0) = |f B 1 | 2 ( l + 2 a ) (50)
T h e t h i r d - o r d e r a p p r o x i m a t i o n h a s b e e n applied by Holt and M o i s e i w i t s c h

(J. P h y s . B_1 (1968) 36) t o t h e e l a s t i c s c a t t e r i n g of e l e c t r o n s by h y d r o g e n
a t o m s . The s u m m a t i o n o v e r all the i n t e r m e d i a t e s t a t e s m in t h e f o r m u l a
f o r f B 2 w a s c a r r i e d out by e x a c t e v a l u a t i o n f o r p r i n c i p a l q u a n t u m n u m b e r s
1, . . . , 5 and by u s i n g t h e c l o s u r e r e l a t i o n given by Schiff (Quantum

M e c h a n i c s (1968) 55).
&ф(г)ф т (г< ) = 6(r -T< ) (51)

m
f o r all t h e h i g h e r s t a t e s including the c o n t i n u u m t a k i n g an a v e r a g e e n e r g y

c o r r e s p o n d i n g to t h e l e v e l with p r i n c i p a l q u a n t u m n u m b e r 6. T h i s is c a l l e d
the simplified second Born approximation.
3.3. H e l i u m a t o m s
C a l c u l a t i o n s of t h e SL = 0,1,2 p h a s e s h i f t s f o r t h e s c a t t e r i n g of e l e c t r o n s
by t h e H a r t r e e field U j i r ) of h e l i u m w e r e f i r s t p e r f o r m e d by M a c D o u g a l l
( P r o c . R. Soc. (London) A136 (1932) 549). S u b s e q u e n t l y , M o r s e and A l l i s
( P h y s . R e v . 4 4 (1933) 269) m a d e allowance f o r e x c h a n g e by u s i n g a
s y m m e t r i z e d f u n c t i o n in c a l c u l a t i o n s f o r t h e Л - 0,1 p h a s e s h i f t s . T h e
s - w a v e phase shifts w e r e also calculated using the variational method,
with and without a l l o w a n c e f o r exchange, by M o i s e i w i t s c h ( P r o c . R. Soc.
(London) A219 (1953) 102).
T h e r o l e of p o l a r i z a t i o n in t h e e l a s t i c s c a t t e r i n g of e l e c t r o n s by h e l i u m
h a s b e e n i n v e s t i g a t e d by C a l l a w a y , L a B a h n , P u , and D u x l e r ( P h y s . Rev. 168
(1968) 12) who solved r a d i a l e q u a t i o n s of t h e f o r m
3 + к i(
{ á * " r2+1> " U
i(r) " U
P ( r ) " U d ( r ) j u s ( r ) = J M r , r - ) u s ( r ' )dr-
° (52)
f o r i = 0,1,2 w h e r e U p (r) is t h e p o l a r i z a t i o n p o t e n t i a l and U d (r) is t h e
d i s t o r t i o n p o t e n t i a l a r i s i n g f r o m the action of t h e k i n e t i c - e n e r g y o p e r a t o r
f o r t h e i n c i d e n t e l e c t r o n on t h e p e r t u r b e d a t o m i c wave f u n c t i o n .
T h e y u s e d t h e following a p p r o x i m a t i o n s :
(a) t h e a d i a b a t i c - e x c h a n g e - d i p o l e (AED) a p p r o x i m a t i o n which i n c l u d e s
only the dipole (Î. = 1) c o m p o n e n t of U p and n e g l e c t s U d ,
(b) the a d i a b a t i c - e x c h a n g e - t o t a l (AET) a p p r o x i m a t i o n which i n c l u d e s
t h e f i r s t t h r e e (I = 0 , 1 , 2 ) m u l t i p o l e c o m p o n e n t s of U p and n e g l e c t s
Ud-
(c) t h e extended p o l a r i z a t i o n (EP) a p p r o x i m a t i o n which i n c l u d e s t h e
f i r s t t h r e e m u l t i p o l e c o m p o n e n t s of U p and the f i r s t two c o m p o n e n t s
(£ = 0,1) of U d .
T h e E P a p p r o x i m a t i o n i s in b e s t a c c o r d with t h e e x p e r i m e n t a l d a t a of
R a m s a u e r and K o l l a t h (Ann. P h y s . 12_ (1932) 529) and of Golden and Bandel
( P h y s . R e v . 1 3 8 (1963) A14). T h e s c a t t e r i n g l e n g t h s they o b t a i n e d w e r e
(a) 1.132a 0 , (b) 1.097 a 0 , (c) 1.151 a,, which all l i e in the r a n g e of v a l u e s
f r o m 1.19 to 1.06 a 0 d e r i v e d by O ' M a l l e y ( P h y s . Rev. 130 (196 3) 1020) f r o m
t h e d a t a of v a r i o u s e x p e r i m e n t e r s . T h e e x p e r i m e n t a l v a l u e d e t e r m i n e d by
Golden and B a n d e l is 1.15 a o
L a B a h n and C a l l a w a y ( P h y s . Rev. 180 (1969) 91 and 188 (1969) 520)
have a l s o u s e d t h e E P a p p r o x i m a t i o n to c a l c u l a t e d i f f e r e n t i a l c r o s s - s e c t i o n s
f o r t h e e l a s t i c s c a t t e r i n g of e l e c t r o n s by h e l i u m . H e r e we c a n c o m p a r e
IAEA - S M R - 1 2 / 1 4 499
with t h e s i m p l i f i e d s e c o n d - B o r n - a p p r o x i m a t i o n c a l c u l a t i o n s to t h e t h i r d
o r d e r of Holt, Hunt, and M o i s e i w i t s c h (J. P h y s . B4 (1971) 1318) and with
t h e c a l c u l a t i o n s of B i r m a n and R o s e n d o r f f (Nuovo C i m . 6 3 B (1969) 89).
They a g r e e quite well with e a c h o t h e r and with t h e e x p e r i m e n t a l d a t a , f o r
e x a m p l e with t h e B r o m b e r g (J. C h e m . P h y s . 5£ (1969) 3906) d a t a at 500 eV.
An i n t e r e s t i n g c o m p a r i s o n c a n b e m a d e f o r the f o r w a r d s c a t t e r i n g
(0 = 0) c a s e . B r a n s d e n and McDowell (J. P h y s . B3 (1970) 29) have u s e d
t h e d i s p e r s i o n r e l a t i o n t o g e t h e r with e x p e r i m e n t a l d a t a on t o t a l c r o s s
s e c t i o n s t o d e t e r m i n e t h e s c a t t e r i n g a m p l i t u d e and d i f f e r e n t i a l c r o s s -
s e c t i o n f o r 0 = 0. Although p o o r a g r e e m e n t is found with the E P a p p r o x i -
m a t i o n v a l u e s of L a B a h n and C a l l a w a y (1969) o v e r the 100-500 eV e l e c t r o n
e n e r g y r a n g e , s a t i s f a c t o r y a c c o r d is obtained with e x p e r i m e n t a l d a t a
e x t r a p o l a t e d to 0 = 0 and with t h e s i m p l i f i e d s e c o n d B o r n c a l c u l a t i o n s of
Holt et al. (1971) t a k e n to the t h i r d o r d e r . In t h e l a t t e r , t h e s u m m a t i o n
o v e r all s t a t e s m in f B 2 w a s c a r r i e d out by e x a c t e v a l u a t i o n f o r the ^ S ,
2 г 3, and 2 X P i n t e r m e d i a t e s t a t e s and by u s i n g the c l o s u r e r e l a t i o n f o r h i g h e r
d i s c r e t e s t a t e s and t h e c o n t i n u u m t a k i n g an a v e r a g e e n e r g y c o r r e s p o n d i n g
to the 3 ^ s t a t e .
3.4. E l a s t i c s c a t t e r i n g of e l e c t r o n s by a t o m i c ions
In the c a s e of the e l a s t i c s c a t t e r i n g of e l e c t r o n s by p o s i t i v e ions with

net c h a r g e Z , it c a n be shown t h a t t h e a s y m p t o t i c f o r m of t h e r a d i a l f u n c t i o n
u ( r ) c o r r e s p o n d i n g to t h e SL = 0 p a r t i a l wave is given by
u ( r ) ~ s i n (kr + - In 2 k r + а + rj) (53)
for large r, where
а = a r g Г Í(^11 -- —
Ž j (54)
Let rj and r)' b e t h e SL = 0 p h a s e s h i f t s f o r e l e c t r o n s with wave n u m b e r s

к and k ' , r e s p e c t i v e l y . T h e n it h a s b e e n shown by B e t h e ( P h y s . Rev. 76
(1949) 38) that
cot n cot n'

2 ir Z l - e x p ( - 2 7 r Z / k ) - 2 z ( l n Ç + q' - q ) = I (k 2 - k' 2 )p (55)
' l-exp(-27rZ/k').
where
Z2 V 1 1
q = (56;
к? L v v* + Z2/k2
u=l
and p i s t h e e f f e c t i v e r a n g e .
T h e c o n t i n u u m s t a t e with wave n u m b e r k' c a n be c o n v e r t e d to a bound
s t a t e with e n e r g y - Z 2 / n ' 2 by putting c o t n 1 = i and k 1 = i Z / n 1 w h e r e n 1 is
the e f f e c t i v e p r i n c i p a l q u a n t u m n u m b e r .
500 MOISEIWITSCH
On d e f i n i n g t h e q u a n t u m d e f e c t ß(n) by
n' = n - ц(п) (57)
w h e r e n i s t h e p r i n c i p a l q u a n t u m n u m b e r , we find ( M o i s e i w i t s c h , P r o c .
P h y s . Soc. 79 (1962) 1166; Seaton, M . N . R . A . S . 118 (1958) 504)
cot Г)
= COt 7Г [Л (n) (58)
1 - exp(-27TZ/k)
f o r s m a l l к and l a r g e n. F r o m this follows t h e f o r m u l a
r)( к = 0) = 7гд(п = oo) (59)
d e r i v e d in a d i f f e r e n t way by Seaton (C.R. A c a d . Sei. P a r i s 240 (1955) 1317).

By c o n s i d e r i n g t h e l s n s ^ S and l s n s 3 S s e r i e s of He, Seaton ( P r o c . P h y s .
Soc. A70 (1959) 620) showed t h a t the p h a s e s h i f t s f o r t h e e l a s t i c s c a t t e r i n g
of e l e c t r o n s by He + ions a r e g i v e n by
r)+(k) = 0.437 - 0.109k 2
ri~(k) = 0.932 - 0.126k 2
w h e r e t h e + and - s i g n s r e f e r to s i n g l e t and t r i p l e t s c a t t e r i n g , r e s p e c t i v e l y .
T h e y a r e in good a g r e e m e n t with t h e I = 0 p h a s e s h i f t s c a l c u l a t e d by
Sloan ( P r o c . Roy. Soc. A2B1 (1964) 151) u s i n g t h e p o l a r i z e d - o r b i t a l s m e t h o d :
к - nj
polarized q-uantvtm
exchange
orbitals defect
0 0.387 0.444 0,437

0.491 0.366 0.424 0.411
0.779 0.341 0.400 0.371
1.076 0.318 0.377 0.311
0 0.920 0.942 0.932

0,491 0.893 0.915 0.902
0.779 0.855 0.875 0.855
1.076 0.802 0.832 0.786
4. E X C I T A T I O N O F ATOMS BY E L E C T R O N I M P A C T
4.1. H y d r o g e n a t o m s
We b e g i n by c o n s i d e r i n g d i r e c t c o l l i s o n s in which t h e wave f u n c t i o n
i s u n s y m m e t r i z e d and e x c h a n g e is n e g l e c t e d .
IAEA - S M R - 1 2 / 1 4 501
T h e d i f f e r e n t i a l c r o s s - s e c t i o n f o r t h e e x c i t a t i o n of t h e n - t h s t a t e of a
h y d r o g e n a t o m i s given in t e r m s of t h e c o r r e s p o n d i n g s c a t t e r i n g a m p l i t u d e
íп(в,ф) by
1 п (0,ф) = | а - К ( 0 , ф ) | 2 (1)
while t h e t o t a l e x c i t a t i o n c r o s s - s e c t i o n is
Qn = ^ y j | f n ( 0 , 0 ) | 2 sin0 d0 d</> (2)
If we n e g l e c t e x c h a n g e and apply the f i r s t B o r n a p p r o x i m a t i o n we obtain
= E ' ^ - Y ^ UN I ( R^ ) DR-^ (3)
_Denoting t h e m o m e n t u m c h a n g e of t h e i n c i d e n t e l e c t r o n b y i i K w h e r e
К = k j - k n and u s i n g B e t h e ' s i n t e g r a l
pit'î' _„ 4- -»
I-* I dr' = Ц г e l K ' r (4)
I r - r' I К.
we find t h a t
f ' V ) = - g ^ e l n ( K ) ( n f l ) (5)
where
e l n (K) = I ^ n ( r ) e i K - r ф ^ г ) d r (6)
t h e t e r m a r i s i n g f r o m t h e e l e c t r o n - p r o t o n i n t e r a c t i o n v a n i s h i n g b e c a u s e of
t h e o r t h o g o n a l i t y of t h e a t o m i c wave f u n c t i o n s .
T h u s we s e e t h a t ( k ^ k ^ I ^ e ,ф) d e p e n d s only on К in the f i r s t B o r n
a p p r o x i m ation.
It i s o f t e n u s e f u l to e x p r e s s in t e r m s of t h e g e n e r a l i z e d o s c i l l a t o r
strength
/M(K)=|? (7)
which s a t i s f i e s t h e s u m r u l e
X /m(K) = 1 (8)
As t h e m o m e n t u m c h a n g e Ж 0, 0 l n ( K ) a p p r o a c h e s t h e o p t i c a l o s c i l l a t o r
s t r e n g t h given by
2
Щ р - (E n - E j ) I í d r \ (9)
w h e r e t h e z c o - o r d i n a t e of the a t o m i c e l e c t r o n is m e a s u r e d in t h e d i r e c t i o n
of K.
Now
K2 = k 2 + k 2 - 2 k 2 k n c o s 0 (10)
and s o
KdK = k o s i n e d0
Hence
in(0,</>)sin0de Ii«,4(к)I2 KdK

(12)
2me4 Д П (К) dK
í č k * E n - E j К
T h e t o t a l c r o s s - s e c t i o n f o r the e x c i t a t i o n of t h e n - t h s t a t e of h y d r o g e n
m a y be w r i t t e n
Qn = (13)
ff / lMK)|2KdK
where
К min
. = k 1 - k íť. Kmax = k 1 + k n (14)
Since by c o n s e r v a t i o n of e n e r g y
k
?"k 2 „ = | | (En-Ej) (15)
we s e e that f o r high e l e c t r o n i m p a c t e n e r g i e s
Kmin^ т Е - О ^ - Щ ) . K m a x S 2k! (16)

IAEA - S M R - 1 2 / 1 4 503
F o r t h e e x c i t a t i o n of t h e 2s and 2p s t a t e s of a t o m i c h y d r o g e n we have
|f(D(K)|2 = 128 ag
( K 2 a 2 0 + f )6
and
288 6 0 m
f ( K )
l ^ l =K (K2a2+J)6
2 (18)
w h e r e m is t h e m a g n e t i c quantum n u m b e r of t h e 2p s t a t e r e f e r r e d to the
m o m e n t u m c h a n g e v e c t o r -ЙК as p o l a r a x i s . T h u s a c c o r d i n g to t h e f i r s t
B o r n a p p r o x i m a t i o n , t h e c r o s s - s e c t i o n s v a n i s h f o r the e x c i t a t i o n of t h e
2p s t a t e s with m = ±1 r e f e r r e d to К as p o l a r a x i s . Also f o r the I s -• 2s
e x c i t a t i o n the d i f f e r e n t i a l c r o s s - s e c t i o n i s weakly d e p e n d e n t upon К f o r
s m a l l a n g l e s of s c a t t e r i n g while f o r t h e I s 2p e x c i t a t i o n it b e h a v e s l i k e K" 2 .
F o r l a r g e a n g l e s of s c a t t e r i n g t h e d i f f e r e n t i a l c r o s s - s e c t i o n s f o r t h e
I s -» 2s and I s ->• 2p e x c i t a t i o n s d e c a y l i k e K"12 and K" 14 a c c o r d i n g to t h e
f i r s t B o r n a p p r o x i m a t i o n which a r e m u c h m o r e r a p i d d e c r e a s e s with angle
than f o r e l a s t i c s c a t t e r i n g (K" 4 ).
We c a n a l s o show t h a t
Q2S ~ 128 (f) 1 0 ТГ/5 k 2 (19)
10 9
Q 2 p ~ 256 ( f ) Trln(4a 0 k 1 )/kj (20)
f r o m which it f o l l o w s t h a t the t o t a l c r o s s - s e c t i o n s f o r t h e I s -» 2s and

I s -» 2p e x c i t a t i o n s d e c a y as E" 1 and E" 1 I n E , r e s p e c t i v e l y , f o r high e l e c t r o n
i m p a c t e n e r g y E.
T h e c r o s s - s e c t i o n f o r the I s -» 2p e x c i t a t i o n , which c o r r e s p o n d s to an
o p t i c a l l y allowed t r a n s i t i o n , i s c o n s i d e r a b l y l a r g e r t h a n t h e c r o s s - s e c t i o n
f o r t h e I s -» 2s e x c i t a t i o n which i s a s s o c i a t e d with an o p t i c a l l y f o r b i d d e n
t r a n s i t i o n . Also t h e peak of t h e I s -» 2p e x c i t a t i o n c r o s s - s e c t i o n o c c u r s at
a higher energy than for the I s 2s e x c i t a t i o n , and d e c a y s l e s s r a p i d l y with
increasing energy.
T h e e i g e n e n e r g y E n of the n - t h l e v e l of a h y d r o g e n a t o m is - 1 / n 2
R y d b e r g s so t h a t f o r l a r g e v a l u e s of n we have
dn = •§• n 3 dE n (21)
Hence t h e c r o s s - s e c t i o n f o r t h e e x c i t a t i o n of a t o m i c h y d r o g e n to all
l e v e l s within t h e r a n g e E n to E n + d E n R y d b e r g s i s given by
Ín3QndE^ (22)
If Q ; ( E ' ) d E ' d e n o t e s t h e c r o s s - s e c t i o n f o r the e j e c t i o n of an e l e c t r o n into

t h e c o n t i n u u m w i t h e n e r g y b e t w e e n E ' and E ' + d E ' R y d b e r g s , it f o l l o w s
t h a t i n 3 Q n , r e g a r d e d a s a f u n c t i o n of E n , is c o n t i n u o u s w i t h Q; (E 1 ) a s
s h o w n by M c C a r r o l l ( P r o c . P h y s . Soc. A70_ (1957) 460).
A s i m p l i f i c a t i o n of t h e firsjt B o r n a p p r o x i m a t i o n i n t r o d u c e d b y B e t h e
c a n b e o b t a i n e d by e x p a n d i n g e l K ' r . C h o o s i n g t h e z - a x i s a l o n g К y i e l d s
€ l i 0 i m ( K ) = 60mJ 0nÊO(^1(?)(l+iKz-èK2z2+...)d? (23)
Setting
-J Фп10(г)^Фг(г)йг (24)
we o b t a i n
c 1 > n { 0 (K) - i K ( z ) l i n { - | K 2 ( z \ n i + . . . (25)
and s o
l 4 1 U K ) i 2 = gjtofcl (z) l i n < i K ( z \ n i + ...P (26)
which converges provided K a o « 1 since a 0 i s the a p p r o x i m a t e r a n g e of t h e

a t o m i c w a v e f u n c t i o n s . F o r K a o » l we note that |fnio(K)| p r o v i d e s a
n e g l i g i b l e c o n t r i b u t i o n t o Qn(!.
We f i r s t c o n s i d e r optically allowed transitions f o r which the final
s t a t e i s a p - s t a t e ( i = 1 ) . T h e n (z) l n í f 0 and we m a y put
2
I ^ K Í N ^ I I Í ^ m J = (27)
I n t e g r a t i n g f r o m K m i n = (m/li 2 kjHEn - E j ) t o K m a x = 2 k x we get
n .. 8^l_(z)i.nt I2 1n 2ft2к2 .
kfa2 m(En - E j ) (i
" (28)
and t h u s t h e I s np excitation c r o s s - s e c t i o n d e c a y s as E"1 I n E f o r l a r g e

E in a c c o r d a n c e w i t h t h e r e s u l t o b t a i n e d in t h e f i r s t B o r n a p p r o x i m a t i o n .
F o r o p t i c a l l y f o r b i d d e n t r a n s i t i o n s ( z ) l n S = 0. If, h o w e v e r , (z2\ n£
d o e s not v a n i s h w e c a n w r i t e
6 Pro
l4 4 m(K)| I (A,, (29)
f o r K a , S 1, and t h e n n e g l e c t i n g t h e c o n t r i b u t i o n f r o m K a 0 > 1 we o b t a i n
IAEA - S M R - 1 2 / 1 4 505
1 (z2)i,nt 1 (30)
Qn к?
1 0
so that the excitation c r o s s - s e c t i o n for a transition I s ns or a quadrupole

transition Is nd d e c a y s l i k e E" 1 as E °° as found p r e v i o u s l y .
We now m a k e a l l o w a n c e f o r e x c h a n g e by e x p r e s s i n g t h e t o t a l s p a t i a l
wave f u n c t i o n in t h e s y m m e t r i z e d f o r m s
f1 Л > = TT X { ¥ m ( ? 2 } ± Fm± i?2

^}} ( 31 )
w h e r e t h e + and - s i g n s a r e a s s o c i a t e d with s i n g l e t and t r i p l e t s c a t t e r i n g ,

r e s p e c t i v e l y . T h e n t h e e n t i r e wave f u n c t i o n of t h e s y s t e m c o m p o s e d of a
spin as w e l l as a s p a c e p a r t i s t o t a l l y a n t i s y m m e t r i c t h u s s a t i s f y i n g t h e
Pauli exclusion principle.
Substituting into t h e S c h r ö d i n g e r equation, m u l t i p l y i n g a c r o s s by
Фп (r 2 ) and i n t e g r a t i n g with r e s p e c t to r 2 y i e l d s
(32)
where
R î n & ) = Fm <?1 ) / У V i ( r a , r 2 )Фт(% ) d? 2 ± фтЪ )J ^ )|v2 )
(33)
with
( 3 4 )
Ъ(гг,г2)
Г
12 1
b e i n g t h e i n t e r a c t i o n e n e r g y b e t w e e n e l e c t r o n 1 and a h y d r o g e n atom
c o m p o s e d of e l e c t r o n 2 and t h e p r o t o n , and
b e i n g t h e i n t e r a c t i o n e n e r g y b e t w e e n e l e c t r o n 2 and a h y d r o g e n a t o m
c o m p o s e d of e l e c t r o n 1 and t h e p r o t o n .
Thus
= Цр X/®'""'71 (36)
m
506 MOISEIWITSCH
T h e 1 ->• n e x c i t a t i o n c r o s s - s e c t i o n s Q^ , Qň c o r r e s p o n d i n g to s i n g l e t
and t r i p l e t s c a t t e r i n g a r e given by
=
Qn i f / / | f n ( M ) | 2 s i n e de dф (57)
and s i n c e they h a v e s p i n s t a t i s t i c a l weighting f a c t o r s i and f , r e s p e c t i v e l y ,

t h e t o t a l 1 ->• n e x c i t a t i o n c r o s s - s e c t i o n is
Q n = i ( Q n + 3Q'„) (38)
T h e B o r n - O p p e n h e i m e r a p p r o x i m a t i o n is given by taking
Fi (r) = e (39)
Fm(r) = 0 (m f 1) (40)
We o b t a i n
-± = 2m
tn e i(k 1 -k n )T 1 ^ ( ^ J V i ^ . E j J ^ C r j J d ? ! dr 2
" " 4тг ~ W
(41)
1
f j e^" "^' Фп1г2)У2$г.ъЩ{гjïd?!«d r ,
the f i r s t t e r m being the Born approximation.

F o r the I s 2s e x c i t a t i o n the B o r n - O p p e n h e i m e r a p p r o x i m a t i o n y i e l d s
a c r o s s - s e c t i o n which, c l o s e to the t h r e s h o l d e n e r g y , i s m u c h l a r g e r t h a n
t h a t given by t h e f i r s t B o r n a p p r o x i m a t i o n . T h u s f o r 1 3 . 6 - e V e l e c t r o n s
(k a = 1), t h e S. = 0 p a r t i a l c r o s s - s e c t i o n given by t h e B o r n - O p p e n h e i m e r
a p p r o x i m a t i o n is 1.59 jrajj, w h e r e a s the m a x i m u m p o s s i b l e c r o s s - s e c t i o n
f o r t h e i - t h o r d e r p a r t i a l wave i m p o s e d by u n i t a r i t y i s {2£ + l ) î r a 2 / k i , and s o
c a n n o t be c o r r e c t . T h i s is a t y p i c a l o c c u r r e n c e f o r S S t r a n s i t i o n s .
The B o r n - O p p e n h e i m e r approximation s u f f e r s f r o m the undesirable
f e a t u r e t h a t t h e addition of a c o n s t a n t to V2 p r o d u c e s a n o n - v a n i s h i n g c h a n g e
in t h e e x c h a n g e s c a t t e r i n g a m p l i t u d e owing to t h e l a c k of o r t h o g o n a l i t y
b e t w e e n the a p p r o x i m a t e f u n c t i o n ^ 1 ( r 1 ) e x p ( i k f r 2 ) d e s c r i b i n g t h e i n i t i a l s t a t e
of t h e s y s t e m and t h e a p p r o x i m a t e f u n c t i o n ^ „ ( г ^ е х р Ц Ц , ' r x ) d e s c r i b i n g the
s t a t e of t h e s y s t e m a f t e r an exchange e v e n t .
T h i s a r b i t r a r i n e s s c a n b e s e e n to a r i s e b e c a u s e (V 2 +kf)Fj v a n i s h e s
f o r F j = e x p f i k } • r ) w h e r e a s it is actually of f i r s t o r d e r in t h e i n t e r a c t i o n
p o t e n t i a l . Thus, n e g l e c t i n g exchange and the c o u p l i n g of t h e initial s t a t e to
all o t h e r s t a t e s , we s e e t h a t
(S728 + k?)F 1 ± (? 2 ) = f r F * ^ ) J K ^ ) ! 2
Vjjft^Jd?! (42)
IAEA - S M R - 1 2 / 1 4 507
which g i v e s f o r t h e s c a t t e r i n g a m p l i t u d e
,±
N
= J _ 2m ei(krkn)• г, фп ( r 2 )Vj ( ï j ,r 2 )ф 1 (г 2 ) d î j dr2
" 4ТГ
(43)
X { V 2 (? a ,r2 ) - J \фу OY )| 2 V2 (r{ ,r2 )dr{ } d í j dr 2
and r e m a i n s u n a l t e r e d if a c o n s t a n t is added to V 2 . T h i s f o r m u l a w a s f i r s t
d e r i v e d by F e e n b e r g ( P h y s . Rev. 40 (1932) 40) and o b t a i n e d in an i m p r o v e d
f o r m by B e l l and M o i s e i w i t s c h ( P r o c . R. Soc. (London) A276 (1963) 346)
who c a l l e d t h e i r f o r m u l a t h e f i r s t - o r d e r e x c h a n g e a p p r o x i m a t i o n . T h e
SL = 0 p a r t i a l c r o s s - s e c t i o n f o r t h e I s 2s e x c i t a t i o n at k j = 1 w a s c a l c u l a t e d
to be 0.39 na.2 by B e l l and M o i s e i w i t s c h u s i n g t h e f i r s t - o r d e r e x c h a n g e
a p p r oxim ation.
An a l t e r n a t i v e a p p r o a c h to t h e p r o b l e m of o v e r c o m i n g t h e i n a d e q u a c i e s
of t h e B o r n - O p p e n h e i m e r a p p r o x i m a t i o n i s due to O c h k u r ( J E T P J_8 (1964)
503), who expanded t h e e x c h a n g e s c a t t e r i n g a m p l i t u d e given by t h e B o r n -
Oppenheimer approximation
g n - - h ^ ř l í * & ) ( 4 - £ ) ) d ? a d ? 2 (44)
in p o w e r s of k j 1 and r e t a i n e d only t h e l e a d i n g t e r m which b e h a v e s as k ' 2 .

T h e e l e c t r o n - p r o t o n i n t e r a c t i o n - e 2 / r 2 g i v e s a c o n t r i b u t i o n which d e c a y s
m o r e r a p i d l y t h a n k"22 and s o i s n e g l e c t e d . Now.
1 piq'(ri-iî) dq
от (45)
47ГГ 12 V
and s i n c e t h e m a i n c o n t r i b u t i o n to g n c o m e s f r o m q - k j , we h a v e to t h e
l o w e s t o r d e r in k j 1
1 47Г -* -*
- . щ Ы г . - г , ) (46)
r e m e m b e r i n g that
Hence
2m e _iK ' r. ( r j )(//j ( r j ) d r j
w h e r e К = k j - k n , giving f o r t h e e n t i r e s c a t t e r i n g a m p l i t u d e a c c o r d i n g to
the Ochkur approximation
(47)
L i k e the f i r s t - o r d e r e x c h a n g e a p p r o x i m a t i o n t h i s h a s t h e v i r t u e t h a t it
r e m a i n s u n a l t e r e d if a c o n s t a n t is added to t h e i n t e r a c t i o n p o t e n t i a l .
We m a y o b t a i n g r e a t e r a c c u r a c y by u s i n g t h e d i s t o r t e d - w a v e s
a p p r o x i m a t i o n w h i c h m a k e s p a r t i a l a l l o w a n c e f o r d i s t o r t i o n of t h e i n c i d e n t
and s c a t t e r e d e l e c t r o n w a v e s . We b e g i n by i n t r o d u c i n g a t w o - s t a t e
a p p r o x i m a t i o n involving t h e g r o u n d s t a t e m = 1 of t h e h y d r o g e n a t o m and
t h e f i n a l s t a t e n. T h e n t h e i n f i n i t e s e t of c o u p l e d e q u a t i o n s r e d u c e s to t h e
p a i r of e q u a t i o n s
2
к + к2 - V „ (?! )} F± ( ? а ) т Ц J К П Ц Д ( F i (?2 ) d? 2
(48)
| r ±f (r2)dr2
\a(*i )}f± / к п п ( ? 1 ( ? 2 ) F n ± & ) dr2
(49)
2m V
ЪР- n l £ ) F / (r1)±f К П Д ,r2)FÍ (r2 )dr 2
where
Vm(?i) - J k (r2) - Ç ) фт(г2) dr2 (50)

42 M
and
e2
Knmťr^r,) + E m +En-E) (51)
If we know t h e s o l u t i o n of t h e r e d u c e d e q u a t i o n
{Vj 2 + k2n - V»»^)}^^) f KJrvr2)^(r2)ár2 - 0 (52)

IAEA - S M R - 1 2 / 1 4 509
with
#;*(?) ~ Г"1 e i k n r /j(0,(/>) (53)
we m a y w r i t e the s c a t t e r i n g amplitude as
f = #
° • Ь W f n±(?l 5 {V"l ^ Knl(?i (?2 ) d ? 2
} (54)
We now i n t r o d u c e the d i s t o r t e d - w a v e s a p p r o x i m a t i o n in which back-coupling

of the final s t a t e n to the initial s t a t e 1 is a s s u m e d to be s m a l l so that
V ln and K l n can be s e t equal to z e r o . Then we have
{vi2 + k 2 - ValÜ £ )Tff- / Ч Д Д ) * ^ )dî 2 = о (55)
where
&~\(v) ~ e ^ i ' 7 + r ' 1 e i k i r /£{в,ф) (56)
Replacing Fj1 by y i e l d s the d i s t o r t e d - w a v e s a p p r o x i m a t i o n
f
n = - b l F I ^ ^ { ^ п А ^ Ц ) ± / K , , ^ ^ ) ^ ) ^ } « ! ? ! (57)
To u s e the d i s t o r t e d - w a v e s method it is n e c e s s a r y to m a k e a p a r t i a l - w a v e s
a n a l y s i s of and in which c a s e the total excitation c r o s s - s e c t i o n Qn
is e x p r e s s e d in t e r m s of p a r t i a l c r o s s - s e c t i o n s . It h a s p r o v e d to be quite
a u s e f u l a p p r o x i m a t i o n and has b e e n applied to the excitation of atomic
hydrogen.
L e t us c o n s i d e r the p a r t i a l - w a v e s a n a l y s i s in d e t a i l without r e f e r e n c e
to the d i s t o r t e d - w a v e s a p p r o x i m a t i o n . We follow the a p p r o a c h of P e r c i v a l
and Seaton ( P r o c . C a m b . P h i l . Soc. 53 (1957) 654).
We s u p p o s e that the a t o m i c - h y d r o g e n e l e c t r o n has the p r i n c i p a l quantum
n u m b e r n and the a n g u l a r - m o m e n t u m quantum n u m b e r s I i . m î . m i and that
the f r e e e l e c t r o n h a s the wave n u m b e r k n and the a n g u l a r - m o m e n t u m
quantum n u m b e r s SL2• m2> angular m o m e n t a of the two e l e c t r o n s
m a y then be coupled to yield the total o r b i t a l a n g u l a r m o m e n t u m with the
quantum n u m b e r s L, M L and the total spin angular m o m e n t u m with the
quantum n u m b e r s S, M s . Since the total o r b i t a l and spin a n g u l a r m o m e n t a
a r e s e p a r a t e l y c o n s e r v e d d u r i n g the collision, t h e i r quantum n u m b e r s
remain unaltered.
Introducing the s p a t i a l function
C
*HMl2s йД) = X 3ÍM У ^ И - Л А ^ <58>
1 2 L
m1(fi Ш2fi
w h e r e Cm,m, Ml i s a C l e b s c h - G o r d a n v e c t o r c o u p l i n g c o e f f i c i e n t , <pal m£ (r)

i s an a t o m i c h y d r o g e n w a v e f u n c t i o n , and Y i m i s a s p h e r i c a l h a r m o n i c , we
m a y expand t h e c o m p l e t e s p a t i a l w a v e f u n c t i o n in t h e s y m m e t r i z e d f o r m s
(?a ,? 2 ) = - Д £ (?! Л ) ± ^ L - M l S ( r 2 , ? ! ) } (59)

v'
w h e r e v d e n o t e s t h e s e t of q u a n t u m n u m b e r s n i 1 i 2 - T h e + s i g n c o r r e s p o n d s
t o s i n g l e t (S = 0) s c a t t e r i n g while the - s i g n c o r r e s p o n d s to t r i p l e t (S = 1)
s c a t t e r i n g . S u b s t i t u t i n g into t h e S c h r ö d i n g e r e q u a t i o n y i e l d s t h e s e t of
c o u p l e d i n t e g r o - d i f f e r e n t i a l e q u a t i o n s f o r t h e r a d i a l f u n c t i o n s F„LS (r)
+
= 0 (60)
v'
L LS
w h e r e t h e V ^ . f r ) a r e p o t e n t i a l i n t e r a c t i o n s and ~WVV. (r) a r e e x c h a n g e i n t e r -
a c t i o n s . T h e s e e q u a t i o n s a r e i n d e p e n d e n t of M L and M s and h a v e no
c o u p l i n g b e t w e e n s t a t e s of d i f f e r e n t L , S q u a n t u m n u m b e r s .
If t h e i n i t i a l s t a t e of t h e whole s y s t e m of e l e c t r o n and H a t o m i s v 1
and t h e f i n a l s t a t e i s v, t h e a s y m p t o t i c b e h a v i o u r of t h e r a d i a l f u n c t i o n
F y (r) m a y b e c h o s e n to h a v e t h e f o r m ( f o r l a r g e r )
F v l s (r) - k ; 4 s i n ( k n r - | i 2 7 r ) ô w . + c o s ( k n r - | i 2 7 r ) K r a , } (61)
or alternatively
F„ ls (r) ~ k ^ í e ^ V - í ^ ) 6W. - e ' i V - ^ i Sw,} (62)
where a r e t h e e l e m e n t s of t h e К m a t r i x ( s o m e t i m e s c a l l e d t h e
r e a c t a n c e m a t r _i x R w i t h e l e m e n t s R vv ,) and S„„.
vv a r e t h e e l e m e n t s of t h e
s c a t t e r i n g m a t r i x S. We s e e t h a t
S = (I_+iK)(I_-iK)" 1 (6 3)
S i n c e К i s r e a l and s y m m e t r i c we h a v e К * = К , К = К and s o
I = S, S* S = I_ (64)
w h i c h m e a n s t h a t t h e s c a t t e r i n g m a t r i x i s s y m m e t r i c and u n i t a r y .
T h e c r o s s - s e c t i o n c a n b e c o n v e n i e n t l y e x p r e s s e d in t e r m s of t h e
t r a n s i t i o n m a t r i x T d e f i n e d by
T = S - I = 2iK (I - i K ) - 1 (65)
IAEA - S M R - 1 2 / 1 4 511
T h u s we h a v e
= a-ntni^n' )
(66)
2 ( 2 ^ + 1)
w h e r e t h e c o l l i s i o n s t r e n g t h is given by
2
Q(nij.n'ij) = I ^T (2S + 1)(2L + 1)I T ( n i 1 l 2 S L , n l &{&'2 SL) (67)
1 г й} SL
Since one cannot s o l v e an i n f i n i t e s e t of coupled e q u a t i o n s , the a t o m i c

s t a t e s which e n t e r t h e e x p a n s i o n of t h e t o t a l wave f u n c t i o n a r e confined to
a few of t h e l o w e s t - l y i n g s t a t e s giving r i s e to a f i n i t e s e t of coupled i n t e g r o -
d i f f e r e n t i a l e q u a t i o n s . T h i s is c a l l e d a c l o s e c o u p l i n g a p p r o x i m a t i o n , t h e
o r d e r of t h e a p p r o x i m a t i o n d e p e n d i n g on t h e a t o m i c s t a t e s which a r e r e t a i n e d
in t h e e x p a n s i o n .
An i n t e r e s t i n g m i n i m u m p r i n c i p l e w a s f i r s t e s t a b l i s h e d by P e r c i v a l
( P h y s . Rev. 119 (1960) 159) with e x c h a n g e n e g l e c t e d u s i n g t h e box
v a r i a t i o n a l m e t h o d and w a s l a t e r g e n e r a l i z e d by Hahn, O' M a l l e y and S p r u c h
( P h y s . Rev. _134 (1964) B397, B911) and by M c K i n l e y and M a c e k ( P h y s .
L e t t . 10^ (1964) .210). T h e proof given by t h e l a t t e r a u t h o r s is b a s e d on t h e
result
(68)
о
w h e r e F is t h e m a t r i x of f u n c t i o n s d e s c r i b i n g t h e m o t i o n of t h e s c a t t e r e d
e l e c t r o n and X is a p a r a m e t e r . As X v a r i e s f r o m 0 to 1, we s u p p o s e t h a t
V e x t e n d s in d i m e n s i o n f r o m n c h a n n e l s to m c h a n n e l s and t h a t t h e m - n
additional c h a n n e l s a r e all c l o s e d . T h e n it c a n b e shown t h a t
(69)
f o r all o r t h o g o n a l m a t r i c e s A, and thus c l o s e d c h a n n e l s c a n only i n c r e a s e

t h e e i g e n p h a s e s . If A is c h o s e n s o t h a t К i s d i a g o n a l i z e d , t h e n it follows
t h a t t h e e i g e n p h a s e s m o n o t o n i c a l l y i n c r e a s e as the s p a c e of c l o s e d c h a n n e l s
is expanded. T h i s i s e x e m p l i f i e d in the c l o s e - c o u p l i n g c a l c u l a t i o n s of t h e
L = 0 s i n g l e t p h a s e s h i f t f o r t h e s c a t t e r i n g of 8 . 2 - e V e l e c t r o n s (k 2 = 0.6)
by atomic hydrogen:
512 MOISEIWITSCH
S t a t e s included
Is 2s 2p 3s 3p phase shift
* 0.6704a
* * 0.7115a
a
* * * 0.7707
3
* * * * 0.7738
* * * * * 0.7814a
b
all s t a t e s 0.894
/
a
Buike and Schey (Phys. Rev. 126 (1962) 141)
b
Schwartz (1961)
The l s - 2 s - 2 p - 3 s - 3 p - 3 d close-coupling approximation has also been

applied by B u r k e , O r m o n d e , and W h i t t a k e r ( P r o c . P h y s . Soc. London £2
(1967) 319) to t h e I s -» 2s and I s ->• 2p e x c i t a t i o n s of a t o m i c h y d r o g e n below
the n = 3 threshold.
A l l o w a n c e f o r coupling to h i g h e r s t a t e s h a s b e e n a c h i e v e d by adding
a n u m b e r of c o r r e l a t i o n t e r m s , which allow e x p l i c i t l y f o r t h e i n t e r e l e c t r o n
s e p a r a t i o n r12, to t h e l s - 2 s - 2 p c l o s e - c o u p l i n g e x p a n s i o n ( B u r k e , T a y l o r ,
P r o c . P h y s . Soc. 88 (1966) 549; T a y l o r , B u r k e ( P r o c . P h y s . Soc. £2 (1967)
336). To i n v e s t i g a t e t h e e f f e c t of this we c o n s i d e r t h e S c h r ö d i n g e r equation
(H - E) Ф = 0 (70)
and i n t r o d u c e t h e F e s h b a c h (Ann. P h y s . ПЭ (1962) 287) p r o j e c t i o n o p e r a t o r s

P and Q d e f i n e d by P + Q = 1, P Q = 0, P 2 = P , Q 2 = Q w h e r e P is c h o s e n to
p r o j e c t onto t h e a t o m i c s t a t e s included in t h e c l o s e - c o u p l i n g e x p a n s i o n .
T h e n we h a v e
P(H - E ) ( P + Q ) \ ř = 0 (71)
Q(H -Е)(Р+<3)Ф = 0 (72)
F r o m (71) we s e e t h a t
P(H - Е)РФ + PHQ\ř = 0 (7 3)
and f r o m (72)
Q(H - E ) Q ^ + QHP-Ф = 0 (74)
so t h a t
Ф = - [Q(H - E ) Q ] _ 1 Q H P i (75)
IAEA - S M R - 1 2 / 1 4 513
Hence
Р(Н-Е)РФ-PHQ[Q(H-E)Q]"1 QHP^ = O (76)
giving
P(H + Vopt - Е ) Р Ф = O (77)
w h e r e the optical potential is given by
Vopt = - PHQ[Q(H -ElQ]" 1 QHP (78)
Introducing eigenfunctions фп of QHQ given by
QHQ ф„=е п ф п (79)
we m a y w r i t e
PHQkX<frn|QHP
V,opt (80)
Z
so that
< » i v k > - - ; [ MgPHQj*n>i'<0 (81)
provided E < e n f o r all n. Hence the optical potential t e r m is a t t r a c t i v e

and gives an i n c r e a s e in the p h a s e s h i f t .
The r e s u l t is i l l u s t r a t e d by the 1 S e l a s t i c s c a t t e r i n g of e l e c t r o n s by
atomic hydrogen at kf = 0.16 f o r which the l s - 2 s - 2 p c l o s e - c o u p l i n g
a p p r o x i m a t i o n gives rjQ = 1.3021, with additional 7 c o r r e l a t i o n t e r m s
gives rjg = 1.412, with 16 c o r r e l a t i o n t e r m s gives г)д = 1.414 (Burke and
T a y l o r , 1966), while S c h w a r t z (1961) found the c o n v e r g e d value rjg = 1.4146
u s i n g the Kohn v a r i a t i o n a l m e t h o d .
B u r k e , G a l l a h e r , and G e l t m a n (J. P h y s . B2 (1969) 1142) and G e l t m a n
and B u r k e (J. P h y s . B £ (1970) 1062) have used the c l o s e - c o u p l i n g method
f o r the s c a t t e r i n g of an e l e c t r o n by a hydrogen atom employing p s e u d o - s t a t e s .
F o r e l a s t i c s c a t t e r i n g the f o r m e r authors u s e d a I s , 2s, 2p expansion
w h e r e the 2p is a p s e u d o - s t a t e which p r o v i d e s full g r o u n d - s t a t e dipole
p o l a r izability.
F o r the excitation of the 2s and 2p s t a t e s n e a r t h r e s h o l d , the l a t t e r
a u t h o r s u s e d a l s , 2s, 2p, 3Š, 3p, 3d c l o s e - c o u p l i n g expansion, the n = 3
p s e u d o - s t a t e s providing full p o l a r i z a b i l i t i e s f o r m o s t of the open c h a n n e l s
above the n = 2 excitation t h r e s h o l d .
The I s -* 2s and I s 2p excitation c r o s s - s e c t i o n s have been m e a s u r e d
by Kauppila, Ott, and F i t e (Phys. Rev. 1. (1970) A1099) and by McGowan,
W i l l i a m s , and C u r l e y (Phys. Rev. 180 (1969) 132), r e s p e c t i v e l y . The
m e a s u r e d Q2P is n o r m a l i z e d to the d a t a of Long, Cox, and Smith (J. R e s .
Natl. B u r . Stand. T2A. (1968) 521) which w a s itself n o r m a l i z e d to t h e B o r n

a p p r o x i m a t i o n plus c o r r e c t i o n f o r c a s c a d e at 200 eV. T h e Q 2s d a t a w e r e
obtained r e l a t i v e to t h a t of Q 2 . The e x p e r i m e n t a l r e s u l t s thus n o r m a l i z e d
l i e about 20% b e l o w t h e c a l c u l a t e d v a l u e s f o r both t h e I s 2s and I s 2p
e x c i t a t i o n c r o s s - s e c t i o n s . H o w e v e r , the t h e o r e t i c a l and e x p e r i m e n t a l
r a t i o s Q 2 s /Q2p a r e r e m a r k a b l y good a g r e e m e n t .
4.2. H e l i u m a t o m s
In t h e c a s e of the e x c i t a t i o n of h e l i u m by e l e c t r o n i m p a c t t h e g e n e r a l i z e d
o s c i l l a t o r s t r e n g t h is given by
2
C ( K ) = f ř ^ h n ( K ) | (82)
where
Cin(K) J e IKz s ф Д Д » ф Д Д ) dr, dr2 (83)

s=1
T h i s is known as t h e l e n g t h f o r m u l a t i o n .
If t h e wave f u n c t i o n s of h e l i u m a r e e x a c t we have
(EJ-EJ-^*! = TFJFV' + V , 2 ) ^ (84)
so that
2
«in») = 2U / e ^ ^ i ^ í ^ V ^ ^ ^ j d ^ d ^
=
1г É ^ W / e i K Z l V
1' ' ^ ] d?2
which y i e l d s
= t: Ё Т Ь ; / e i K 4 2 iK n
* -к2 ^ * 0 (85)
S i m i l a r l y we c a n show t h a t
e
in (K) = Sr E T W / +
(86)
IAEA - S M R - 1 2 / 1 4 515
and t h u s , by addition, we find t h a t
iK - Э^
(87)
-in ( K ) = ^
m E1-Er ч п
Эг,
and t h i s is known as t h e v e l o c i t y f o r m u l a t i o n .
The l e n g t h and v e l o c i t y f o r m u l a s a r e t h e s a m e f o r e x a c t f u n c t i o n s .
H o w e v e r , t h e u s e of a p p r o x i m a t e wave f u n c t i o n s l e a d s to e r r o r and to
d i f f e r e n c e s b e t w e e n t h e r e s u l t s given by t h e two f o r m u l a t i o n s .
C a l c u l a t i o n s h a v e b e e n p e r f o r m e d by Kennedy and K i n g s t o n (J. P h y s .
B H 1 9 6 8 ) 195) on the ^ S - 2 J P e x c i t a t i o n u s i n g t h r e e d i f f e r e n t p a i r s of
w a v e f u n c t i o n s . T h e m o s t a c c u r a t e ground s t a t e wave f u n c t i o n u s e d w a s
t h e 6 - p a r a m e t e r f u n c t i o n of S t e w a r t and Webb ( P r o c . P h y s . Soc. £2 (196 3)
532). F o r t h i s c a l c u l a t i o n the l e n g t h and v e l o c i t y r e s u l t s a g r e e to b e t t e r
t h a n 1% o v e r m o s t of t h e e n e r g y r a n g e and a r e in good a g r e e m e n t with
t h e r e l a t i v e v a l u e s of t h e g e n e r a l i z e d o s c i l l a t o r s t r e n g t h m e a s u r e d by
L a s s e t t r e , K r a s n o w , and S i l v e r m a n (J. C h e m . P h y s . 40 (1964) 1242) and
S i l v e r m a n and L a s s e t t r e (J. C h e m . P h y s . 40 (1964) 1265).
S i m i l a r c a l c u l a t i o n s e m p l o y i n g both t h e l e n g t h and v e l o c i t y f o r m u l a t i o n s
w e r e p e r f o r m e d by Bell, Kennedy, and Kingston (J. P h y s . Bl_ (1968) 204)
f o r t h e e l e c t r o n e x c i t a t i o n of g r o u n d - s t a t e h e l i u m to t h e n J P (n = 2 , , . . , 6 )
and n 1 D (n = 3 , . . . , 6 ) s t a t e s and c o m p a r e d with t h e e x p e r i m e n t a l d a t a of
M o u s t a f f a M o u s s a ( T h e s i s , Univ. of L e i d e n (1967)) but a g r e e m e n t is p o o r
at high e l e c t r o n i m p a c t e n e r g i e s . B e l l and K i n g s t o n (J. P h y s . Bl_ (1968)
521) also u s e d the l e n g t h and v e l o c i t y f o r m u l a t i o n s to c a l c u l a t e c r o s s - .
s e c t i o n s f o r the e x c i t a t i o n of t h e g r o u n d - s t a t e h e l i u m to the 2 1 S and 3 ^
s t a t e s . T h e t h e o r y is in good a g r e e m e n t with t h e e x p e r i m e n t a l d a t a of
M o u s t a f f a M o u s s a (1967) f o r t h e 3 1 S e x c i t a t i o n but t h e e x p e r i m e n t a l d a t a of
Van den Bos ( T h e s i s , Univ. of A m s t e r d a m (1967)) a r e about 60% g r e a t e r
t h a n the B o r n a p p r o x i m a t i o n .
C a l c u l a t i o n s u s i n g t h e s i m p l i f i e d second B o r n a p p r o x i m a t i o n t a k e n to
t h e t h i r d o r d e r h a v e b e e n p e r f o r m e d by Holt, Hunt and M o i s e i w i t s c h (1971).
T h e y find t h a t t h e e f f e c t of coupling to h i g h e r s t a t e s is not i m p o r t a n t f o r
t h e 1 1 S 2 1 S and 1 J S -» 2 г Р e x c i t a t i o n s of h e l i u m at e n e r g i e s a s g r e a t a s
500 eV. T h i s p r o v i d e s t h e e x p l a n a t i o n f o r t h e good a c c u r a c y of t h e f i r s t
B o r n a p p r o x i m a t i o n and the d e p e n d e n c e of the d i f f e r e n t i a l c r o s s - s e c t i o n
only on K 2 and not on к at h i g h e r e n e r g i e s as p r e d i c t e d by t h e f i r s t B o r n
approximation.
A close-coupling 11S-21S-21P-23S-23P calculation has been p e r f o r m e d
by B u r k e , C o o p e r , and O r m o n d e ( P h y s . Rev. L e t t . 17. (1966) 345) and
( P h y s . Rev. 183 (1969) 245). T h e i r r e s u l t s f o r the e x c i t a t i o n c r o s s - s e c t i o n s
a r e in s a t i s f a c t o r y a c c o r d a n c e with e x p e r i m e n t a l d a t a (Schulz, F o x , P h y s .
Rev. 106 (1957) 1179; Holt, K r o t k o v , P h y s . Rev. 144 (1966) 82). T h e
m e t a s t a b l e 21S 2 3 S c o n v e r s i o n c r o s s - s e c t i o n h a s a l s o b e e n c a l c u l a t e d
by B u r k e et al. (1966) and is in a g r e e m e n t with the e x p e r i m e n t a l point
obtained by P h e l p s ( P h y s . Rev. 99 (1955) 1307).
F u r t h e r d e t a i l s c o n c e r n i n g t h e s c a t t e r i n g of e l e c t r o n s by a t o m s c a n
be found in t h e a r t i c l e by M o i s e i w i t s c h and S m i t h ( E l e c t r o n I m p a c t E x c i t a t i o n
of A t o m s , Rev. Mod. P h y s . 40 (1968) 238) and by Mott and M a s s e y (1965).
5. RESONANCES
5.1. Single channel S - m a t r i x theory
We s u p p o s e t h a t t h e r e i s an i s o l a t e d p o l e of S 4 (k) n e a r t o t h e r e a l
k - a x i s , and l e t i t s p o s i t i o n b e g i v e n b y
kf = E r - l i T (1)
T h e n t h e r e i s a z e r o of S t ( k ) at E r i r and s o if w e s u p p o s e t h a t a l l t h e
o t h e r s i n g u l a r i t i e s of Sj a r e f a r away we c a n w r i t e f o r E c l o s e to E r
where is a s l o w l y v a r y i n g p h a s e s h i f t . T h u s t h e r e s o n a n t c o n t r i b u t i o n
to t h e t o t a l p h a s e s h i f t i s
(3)
and s o t h e p a r t i a l c r o s s - s e c t i o n t a k e s the f o r m
Qi = - p (2Л + 1) s i n 2 (i)J + T)j )
p- {21 + 1) sin 2 sin2nj (cotnJ+cotn°)2
2
ij Y
l (21
too +
4.11
1 ) s„1
i n 2 щ 0(e+q) (4)
k 2
l+€
where
e = = -coW (5)
? J- *
and
q = -cot щ (6)
Thus
Q t = Q ^ (7)
where
(2je + l ) s i n 2 r ) ° (8)
IAEA - S M R - 1 2 / 1 4 517
5.2. Shape r e s o n a n c e s
A s h a p e r e s o n a n c e is one which a r i s e s f r o m the s h a p e of t h e p o t e n t i a l

and is o f t e n s u p p o r t e d by t h e a n g u l a r - m o m e n t u m b a r r i e r .
Now
_ 2i t a n r)t
i{ 1
"1-itann, '
= 2i
cot r){ " i
and thus a r e s o n a n c e is s e e n to o c c u r when cot ri i = i.

A s s u m i n g t h a t t h e s h a p e r e s o n a n c e o c c u r s at a s u f f i c i e n t l y low e n e r g y
to u s e the B l a t t - J a c k s o n f o r m u l a
k 2 s + 1 c o t r)t = + i r 0 „ k2 (10)
cLg Z
we obtain
jjj2£+ 1 = _ + 1. r 0 { k 2 (11)
ац ь
w h e r e к 2 = к 2 - \ i Г. Thus
к, = —-—
a r
(12)
{ 0î
and
r0{ r0{ V &H r 0 {
Further
2 ik2c +1
T- - r>=
1
1
- i + i rr kk 2 - i k 2 i + 1
a, 2 o« ^
(14)
i Г
s o t h a t t h e width of t h e r e s o n a n c e is Г and i t s p o s i t i o n is E r = k 2 .
As an e x a m p l e we c o n s i d e r t h e 3 P (Í = 1) s c a t t e r i n g of e l e c t r o n s by
n i t r o g e n a t o m s . C l o s e - c o u p l i n g c a l c u l a t i o n s h a v e b e e n p e r f o r m e d by
H e n r y , B u r k e , and Sin F a i L a m ( P h y s . Rev. Г78 (1969) 218) who found a
s h a p e r e s o n a n c e at E r = 0.066 Ry r e f e r r e d to the 4 S g r o u n d s t a t e of n i t r o g e n ,
with a width Г = 0,047 Ry. H o w e v e r , t h e e f f e c t of h i g h e r s t a t e s is i m p o r t a n t
518 MOISEIWITSCH
but has b e e n n e g l e c t e d in t h i s c l o s e - c o u p l i n g a p p r o x i m a t i o n . Hunt and

M o i s e i w i t s c h (J. P h y s . Вjí (1970) 892) u s e d a m o d e l p o t e n t i a l
( r s с)
(57)
U(r) = 0 r ž с
with Z = 7 and с = 1.097 obtained by e x t r a p o l a t i o n along t h e a p p r o p r i a t e

i s o e l e c t r o n i c s e q u e n c e of p o s i t i v e ions u s i n g e x p e r i m e n t a l e n e r g y l e v e l
d a t a . T h e y fotind a s h a p e r e s o n a n c e f o r t h i s c a s e at E r = 0.017 Ry with
width Г = 0.0021 Ry, the c o n s i d e r a b l e d i s p l a c e m e n t of t h e r e s o n a n c e being
t h e r e s u l t of the p o l a r i z a t i o n a r i s i n g f r o m coupling to h i g h e r s t a t e s .
5.3. F ano t h e o r y
C e r t a i n t y p e s of r e s o n a n c e s which o c c u r in t h e s c a t t e r i n g of e l e c t r o n s
by a t o m s r e s u l t f r o m the i n t e r a c t i o n of d i s c r e t e s t a t e s with the c o n t i n u u m .
T h i s h a s b e e n i n v e s t i g a t e d by F a n o ( P h y s . Rev. 124 (1961) 1866).
We l e t I ф У b e t h e z e r o - o r d e r a p p r o x i m a t i o n wave f u n c t i o n d e s c r i b i n g
t h e d i s c r e t e s t a t e and l e t |0(E))> r e p r e s e n t t h e continuum s t a t e with the
e n e r g y E . We a s s u m e t h a t t h e s e f u n c t i o n s a r e n o r m a l i z e d and o r t h o g o n a l :
<ф|ф> = 1 (16)
<ф\ф( E ) > = 0 (17)
0 ( E - )\ф(Е)> = ô(E'-E) (18)
If H is t h e H a m i l t o n i a n of the s y s t e m we h a v e
<ф[н|ф> = E» (19)
w h e r e E 0 is the e n e r g y of t h e d i s c r e t e s t a t e ; we w r i t e
<0{E)[H|</>> = V(E) (20)
and we a s s u m e t h a t
0(E')|h|(Í/(E)> = E è (E'-E) (21)
We now d i a g o n a l i z e H in t h e s p a c e d e f i n e d by | ф У and by
introducing the eigenfunction
| ф ( Е ) > = а | ф > + j T d E - b ( E ' ) I .ACE' ) > (22)

IAEA - S M R - 1 2 / 1 4 519
Then
<</>|Н|Ф(Е)> = Е < Ф | Ф ( Е ) > = ЕЕ (23)
and
<^(Е')|н|ф(Е)>= Е<>(Е')|ф(Е)> = Eb(E') (24)
Also
< ф | н | ф ( Е ) > = а<ф|Щ>> + J d E ' Ь ( Е ' ) < ф | н | ^ ( Е ' ) >
аЕ + / d E ' b ( E ' ) V(E') (25)
and
< ^ ( Е ' ) | н | ф ( E ) > = а < ^ ( Е ' ) | н | ф > + ^f d E " b ( E " ) 0 ( E ' ) | H | < / / ( E M ) >
V(E') + E ' b ( E ' ) (26)
Hence
E 0 + / d E ' b ( E ' ) V(E') = E a (27)
aV(E') + E ' b ( E ' ) = E b ( E ' ) (28)
so t h a t
1
b ( E ' ) = aV(E' ) + Z(E)6(E - E ' ) (29)
E-E1
w h e r e Z(E) d e p e n d s on t h e c o n t o u r of i n t e g r a t i o n r o u n d t h e s i n g u l a r i t y at
E , and P d e n o t e s t h e p r i n c i p a l v a l u e .
Suppose t h a t f o r l a r g e r
ф(E) ~ s i n (k(E) r + n 0 (E)} (30)
w h e r e r)0(E ) is a slowly v a r y i n g p h a s e s h i f t . Then
dE
ф ( Е ) ~ J dE' b ( E ' № ( E ' ) ~ aV(E) s i n { k ( E ' ) r + no(E')}
E-E'
+ Z(E) s i n {k(E)r + n 0 (E)}
= aV(E)[-Tr c o s { k ( E ) r + r) 0 (E)} + Z ( E ) s i n { k ( E ) r + n 0 (E)} ] (31)

t h e i n t e g r a l b e i n g e v a l u a t e d by c h o o s i n g a p p r o p r i a t e c o n t o u r s in the c o m p l e x
E - p l a n e . Thus
Ф(Е) ~ s i n { k ( E ) r + n 0 (E) + R7r(E)} (32)
where
Пг (E) = -tan"- l . (33)

Z(E)
A l s o we have
a E 0 + a j dE' | V ( E ' ) | 2 | P + Z(E)6(E-E' = Ea (34)
so that
+ F J dE.[v(E:)f + z ( E ) | v ( E ) | 2 = E
(35)
and t h u s
(36)
I V(E) V(E)|
where
dE' I V(E' ) I
Д (E) = P (37)
E -E'
We now s e e that the r e s o n a n t p h a s e s h i f t r) r (E) i n c r e a s e s r a p i d l y t h r o u g h

7r n e a r t h e r e s o n a n c e e n e r g y E r = E® + Д Е , and t h e r e s o n a n c e width is given
by
Г = -2(E -Er)tannr(E)
= 2тг(Е-Et)/Z(E)
2тг I V(E ) I (38)
F a r t h e r a n a l y s i s l e a d s to a l i n e p r o f i l e of t h e s a m e s h a p e a s d e r i v e d
previously
(д + е Г (39)
1 +e2
IAEA - S M R - 1 2 / 1 4 521
w h e r e e = - c o t rj r = (E - E r ) / l r , and q i s c a l l e d t h e l i n e - p r o f i l e i n d e x . The
c r o s s - s e c t i o n then t a k e s the f o r m
Q = Q a - ^ f f + Qb (40)
5.4. Dipole r e s o n a n c e s
In t h e a s y m p t o t i c r e g i o n o u t s i d e a r a n g e r Q of t h e o r d e r of t h e a t o m i c
d i m e n s i o n s t h e c o u p l e d e q u a t i o n s d e s c r i b i n g t h e s c a t t e r i n g of e l e c t r o n s by
atomic hydrogen read
(r>ro) (41)
w h e r e the m a t r i x a couples d e g e n e r a t e s t a t e s with principal quantum

n u m b e r n and a n g u l a r - m o m e n t u m q u a n t u m n u m b e r s d i f f e r i n g b y 1 s u c h
a s t h e 2s and 2p s t a t e s of H.
T h i s e q u a t i o n c a n be t r a n s f o r m e d to
d2 X(X + 1 ) , i 2 I д-1.
+ k
dr2 nJ ň F = 0 (42)
w h e r e X(X + 1) i s d i a g o n a l and i s g i v e n by
A" 1 { i ( i + 1) + <*} A = X(X + 1) (43)
P u t t i n g X(X + 1 ) = a w e s e e t h a t
X = - | + ( | + a y (44)
T h e t h r e s h o l d b e h a v i o u r of |T(V,I/' ) | 2 , w h e r e T i s t h e t r a n s i t i o n m a t r i x ,
i s g i v e n by |k„ + ^| 2 s o t h a t , p r o v i d e d X + -j i s r e a l , t h e p a r t i a l c r o s s - s e c t i o n
f o r t h e v<-* v e x c i t a t i o n v a n i s h e s a s kn-> 0. H o w e v e r , if t h e r e a r e n e g a t i v e
v a l u e s of a < - 1 / 4 t h e n X + \ = iß w h e r e ß i s r e a l s o t h a t
|kx+i|2 = j k ifi |2 = x (45)
w h i c h m e a n s t h a t t h e e x c i t a t i o n c r o s s - s e c t i o n r e m a i n s f i n i t e in t h e
n e i g h b o u r h o o d of t h e t h r e s h o l d . M o r e o v e r , a < - l / 4 : i s the c o n d i t i o n t h a t
t h e d i f f e r e n t i a l e q u a t i o n w i l l p o s s e s s an i n f i n i t e n u m b e r of b o u n d s t a t e s
w h i c h b e c o m e r e s o n a n c e s w h e n c o u p l e d to o p e n c h a n n e l s . T h e y a r e c a l l e d
dipole r e s o n a n c e s . They have been o b s e r v e d just below the n = 2 t h r e s h o l d
by M c G o w a n , C l a r k e , and C u r l e y ( P h y s . R e v . L e t t . 15 (1965) 917) who
s t u d i e d t h e e l a s t i c s c a t t e r i n g of e l e c t r o n s by a t o m i c h y d r o g e n at a n g l e s of 90°.
In t h e c a s e of 2 s - 2 p coupling f o r s - w a v e e l e c t r o n - h y d r o g e n s c a t t e r i n g
t h e coupled e q u a t i o n s a r e a s y m p t o t i c a l l y
= 0 (46)
+k
( è l ) F 2 s - J 2 F 2p = 0 (47)
so that
б' ~oj <48>
which y i e l d s the e i g e n v a l u e s X(X + 1) = 1± 4Wf, one of which p r o v i d e s the

c o m p l e x v a l u e X = - i + iî with д = ( - / з Т - 5 / 4 ) г .
The coupling of d e g e n e r a t e c h a n n e l s by a dipole i n t e r a c t i o n w a s f i r s t
e x a m i n e d by G a i l i t i s and D a m b u r g ( P r o c . P h y s . Soc. 82 (1963) 192).
B u r k e and Schey (1962) found a ^ r e s o n a n c e in e l e c t r o n - h y d r o g e n
e l a s t i c s c a t t e r i n g u s i n g t h e l s - 2 . s - 2 p c l o s e - c o u p l i n g a p p r o x i m a t i o n . It
o c c u r s at 9.56 eV and h a s a width of 0.0475 eV, F u r t h e r r e s o n a n c e s in
t h e S, P , D w a v e s h a v e s i n c e b e e n found below t h e n = 2 t h r e s h o l d at
10.2 eV.
T h e l s - 2 s - 2 p - 3 s - 3 p - 3 d c l o s e - c o u p l i n g c a l c u l a t i o n s of B u r k e , O r m o n d e
and W h i t t a k e r (1967) y i e l d Is-* 2s and l s - " 2 p e x c i t a t i o n c r o s s - s e c t i o n s which
show r e s o n a n c e s j u s t b e l o w t h e n = 3 t h r e s h o l d at 12.1 eV.
T a y l o r and B u r k e ( P r o c . P h y s . Soc. (1967) 336) have u s e d t h e
l s - 2 s - 2 p c l o s e - c o u p l i n g a p p r o x i m a t i o n with 20 c o r r e l a t i o n t e r m s to
i n v e s t i g a t e t h e I s - 2s and I s -» 2p e x c i t a t i o n s of a t o m i c h y d r o g e n j u s t
above t h e n = 2 e x c i t a t i o n t h r e s h o l d . N a r r o w Х Р s h a p e r e s o n a n c e s a r e
found in both c a s e s . If t h e I s -» 2s c r o s s - s e c t i o n is folded with a b e a m of
G a u s s i a n s h a p e and 0.2 eV width, good a g r e e m e n t is obtained with t h e
e x p e r i m e n t a l d a t a of L i c h t e n and Schultz ( P h y s . Rev. П £ (1959) 1132).
L i k e w i s e , if t h e I s 2p c r o s s - s e c t i o n i s folded with an e x p e r i m e n t a l
e l e c t r o n d i s t r i b u t i o n of a p p r o p r i a t e s h a p e , good a c c o r d a n c e is obtained
with the e x p e r i m e n t a l d a t a of C h a m b e r l a i n , Smith, and Heddle ( P h y s . Rev.
L e t t . 12 (1964) 647). T h i s J P r e s o n a n c e h a s a l s o b e e n o b s e r v e d by
McGowan and W i l l i a m s ( P h y s . Rev. L e t t . 21_ (1968) 719) with 0.07 eV
resolution.
Next we c o n s i d e r t h e s c a t t e r i n g of e l e c t r o n s by h e l i u m . Schulz ( P h y s .
Rev. L e t t . 10 (1963) 104) o b s e r v e d a n a r r o w r e s o n a n c e at 19.3 eV, lying
about 0.5 eV below t h e 2 3 S t h r e s h o l d , in t h e e l a s t i c s c a t t e r i n g of e l e c t r o n s
in h e l i u m at 72°. A n d r i c k and E h r h a r d t (Z. P h y s i k L92 (1966) 99) c a r r i e d
out a n g u l a r - d i s t r i b u t i o n m e a s u r e m e n t s which showed that the r e s o n a n c e
o c c u r s in t h e 2 S s t a t e and c a n be a s s i g n e d to the He" I s 2s 2 c o n f i g u r a t i o n .
T h i s r e s o n a n c e w a s a l s o found by Kuyatt, S i m p s o n , and M i e l c z a r e k ( P h y s .
R e v . 138 (1965) A385) in an e l e c t r o n t r a n s m i s s i o n e x p e r i m e n t . It is a
closed-channel or Feshbach resonance.
N a r r o w r e s o n a n c e s in t h e 2 3 S e x c i t a t i o n c r o s s - s e c t i o n of h e l i u m j u s t
above t h r e s h o l d w e r e found by Schulz and P h i l b r i c k ( P h y s . Rev. L e t t .
(1964) 477) at 72°. Also C h a m b e r l a i n and H e i d e m a n n ( P h y s . R e v . L e t t .
IAEA - S M R - 1 2 / 1 4 523
1_5_(1965) 337) h a v e m e a s u r e d t h e n = 2 e x c i t a t i o n c r o s s - s e c t i o n s of h e l i u m
in t h e f o r w a r d d i r e c t i o n . R e s o n a n c e s w e r e o b s e r v e d which a r e r e l a t e d to
t h e dipole r e s o n a n c e s in e l e c t r o n - h y d r o g e n s c a t t e r i n g . T h e p e a k s at
19.95 eV, 20.45 eV, and 21.00 eV in the 2®S e x c i t a t i o n c r o s s - s e c t i o n h a v e
b e e n shown by t h e a n g u l a r - d i s t r i b u t i o n m e a s u r e m e n t s r a n g i n g f r o m 7° to
110° of E h r h a r d t and W i l l m a n n (Z. P h y s i k 203 (1967) 1) to be n e a r l y p u r e
S, P , and D - w a v e s c a t t e r i n g , r e s p e c t i v e l y . F u r t h e r t h e 1 1 S - 2 3 S - 2 1 S - 2 3 P - 2 1 P
c l o s e - c o u p l i n g c a l c u l a t i o n s of B u r k e , C o o p e r , and O r m o n d e (1966) exhibit
a 2 P r e s o n a n c e at 20.4 eV, a 2 D r e s o n a n c e at 21 eV and a 2 F r e s o n a n c e at
a h i g h e r e n e r g y c o n f i r m i n g the o b s e r v e d 2 P and 2 D r e s o n a n c e s . T h e 2 S -
peak is the t a i l of t h e 19.3 eV r e s o n a n c e .
C l o s e d - c h a n n e l o r F e s h b a c h r e s o n a n c e s a r i s i n g f r o m doubly e x c i t e d
s t a t e s w e r e f i r s t o b s e r v e d by Widdington and P r i e s t l e y ( P r o c . R. Soc.
(London) A145 (1934) 462) and s u b s e q u e n t l y with h i g h e r e n e r g y r e s o l u t i o n
by S i l v e r m a n and L a s s e t t r e (J. C h e m . P h y s . 4 £ (1964) 1265) and S i m p s o n ,
M i e l c z a r e k , and C o o p e r (J. Opt. Soc. Am. 54_(1964) 269) as p e a k s in the
e n e r g y l o s s s p e c t r u m of e l e c t r o n s in h e l i u m c o r r e s p o n d i n g to t h e 2 s 2 p 1 P
and h i g h e r doubly e x c i t e d 1 P - s t a t e s .
We now d i r e c t o u r a t t e n t i o n to t h e s c a t t e r i n g of e l e c t r o n s by H e + - i o n s
which h a s b e e n i n v e s t i g a t e d by B u r k e and M c V i c a r ( P r o c . P h y s . Soc. 86
(196 5) 989) u s i n g t h e l s - 2 s - 2 p c l o s e - c o u p l i n g a p p r o x i m a t i o n at e n e r g i e s
below t h e n = 2 t h r e s h o l d . A s e r i e s of r e s o n a n c e l e v e l s w e r e found
c o r r e s p o n d i n g to doubly e x c i t e d s t a t e s ^ S S S , 1 ? , 3 ? ) of h e l i u m . They a r e
in good a g r e e m e n t with t h e e x p e r i m e n t a l d a t a of Madden and Codling
( P h y s . Rev. L e t t . 10 (1963) 516 and A s t r o p h y s . J . L41 (1965) 364) on t h e
1
P r e s o n a n c e s who c a r r i e d out a b s o r p t i o n s p e c t r o s c o p y on h e l i u m u s i n g
a c o n t i n u o u s UV s o u r c e in t h e 180-470 A r e g i o n , and with t h e d a t a of Rudd
( P h y s . Rev. L e t t . _13 (1964) 503 and P h y s . Rev. L e t t . j_5 (1965) 580) on t h e
2sns 1 S, 2 s n p 3 P r e s o n a n c e s e x c i t e d by f a s t ion b e a m s ; Rudd o b s e r v e d
e l e c t r o n s e m i t t e d at 160° to the incident b e a m d i r e c t i o n a r i s i n g f r o m t h e
auto i o n i z a t i o n of t h e doubly e x c i t e d s t a t e s of h e l i u m .
T h e M a d d e n - C o d l i n g r e s o n a n c e s have t h e t y p i c a l s h a p e p r e d i c t e d by
F a n o (1961) f o r n e g a t i v e l i n e - p r o f i l e index q(= - 2 . 6 5 f o r г в г р ^ ) . T h e y
found one b r o a d s e r i e s and one f a i n t s e r i e s . C o o p e r , F a n o , and P r a t s
( P h y s . Rev. L e t t . 10 (1963) 518) explained t h i s by i n t r o d u c i n g z e r o - o r d e r
s t a t e s (2snp ± г р п в р Р . T h e + s e r i e s is about 100 t i m e s b r o a d e r than the
narroVv s e r i e s . T h i s a r i s e s b e c a u s e the o v e r l a p i n t e g r a l with t h e l s k p 1 ?
continuum i s m u c h g r e a t e r in t h e + s t a t e s t h a n in t h e - s t a t e s . L i k e w i s e
we have (2snp ± 2 p n s p P z e r o - o r d e r s t a t e s with the + s e r i e s b e i n g m u c h
b r o a d e r than the - s e r i e s .
I n t e r e s t i n g w o r k h a s a l s o b e e n c a r r i e d out by Rudd and Smith ( P h y s .
Rev. 169 (1968) 79), on autoionizing e l e c t r o n s f r o m a t o m i c oxygen. Good
a g r e e m e n t w a s found b e t w e e n t h e o b s e r v e d p o s i t i o n s of t h e autoionizing
l e v e l s of О e x c i t e d by 100 keV H + and He + ions and t h e p o s i t i o n s c a l c u l a t e d
using a 4 S - 2 D - 2 P close-coupling approximation for e - 0 + scattering.
IAEA-SMR-12/17,19
ANALYSIS O F E L E C T R O N - A T O M S C A T T E R I N G
AND P H O T O I O N I Z A T I O N P R O C E S S E S
P.G. BURKE
Queen's University,
Belfast, Northern Ireland,
United Kingdom
Abstract
ANALYSIS OF ELECTRON-ATOM SCATTERING AND PHOTOIONIZATION PROCESSES.

The paper deals with low-energy scattering theory and analysis of experimental results. 1. The
scattering matrix and the collision cross-section; 1 . 1 . Introduction; 1 . 2 . Partial wave analysis;
1 . 3 . Fine-structure transitions; 2. The close-coupling approximation and some recent developments;
2 . 1 . Introduction; 2 . 2 . The close-coupling equations; 2 . 3 . The inclusion of higher channels; 3. Low-
energy electron-atom scattering; 3. Low-energy electron-atom scattering; 3 . 1 . Introduction; 3 . 2 . Electron
scattering by atomic hydrogen; 3 . 3 . Electron scattering by singly ionized helium ; 3 . 4 . Electron scattering
by alkali metal atoms; 3. 5. Electron scattering by np^ atoms and ions; 4 . Atomic photoionization processes;
4 . 1 . Introduction; 4 . 2 . Theory of photoelectron angular distributions; 4 . 3 . Recent results for the total cross-
section and the asymmetry parameter; 4 . 4 . Resonances in photoionization processes; 4 . 5. Production of spin
polarized electrons.
1. T H E S C A T T E R I N G M A T R I X AND T H E COLLISION
CROSS-SECTION
1.1. Introduction
We will c o n s i d e r f i r s t the s i t u a t i o n w h e r e an e l e c t r o n i s i n c i d e n t
u p o n an a t o m , which i s in s o m e s t a t e d e n o t e d by the w a v e f u n c t i o n ф( .
A f t e r the c o l l i s i o n t h e a t o m m a y be l e f t in a n o t h e r s t a t e d e n o t e d b y </>j
and the s c a t t e r e d e l e c t r o n ' s e n e r g y c h a n g e d c o n s i s t e n t with the p r i n c i p l e
of c o n s e r v a t i o n of e n e r g y . T h e a s y m p t o t i c f o r m of t h e t o t a l w a v e f u n c t i o n
is then
i k z J f
*1 ~ ф1 ^ e i + ) V * ™ i Ji ( е , ф ) ^ (1)
r oo 2 L I J i r
j
s n
w h e r e x^yîj P i f u n c t i o n of the s c a t t e r e d e l e c t r o n , w h e r e t h e d i r e c t i o n
of s p i n q u a n t i z a t i o n i s u s u a l l y t a k e n to be the i n c i d e n t b e a m d i r e c t i o n , and
w h e r e 1^(в,ф) i s t h e s c a t t e r i n g a m p l i t u d e . T h e wave n u m b e r k j i s r e l a t e d
to t h e t o t a l e n e r g y of t h e e l e c t r o n - a t o m s y s t e m b y
E = E j + i kf (2)
w h e r e E f i s the e n e r g y of t h e a t o m i c s t a t e .
A l t h o u g h , f o r m a l l y , i o n i z a t i o n can be i n c l u d e d in E q . (1) by a l l o w i n g
t h e s u m m a t i o n o v e r j to i n c l u d e the c o n t i n u o u s s p e c t r u m of t h e a t o m i c
H a m i l t o n i a n , the s i t u a t i o n in t h i s c a s e is c o m p l i c a t e d b y the b o u n d a r y
525
526 BURKE
c o n d i t i o n s s a t i s f i e d by the s c a t t e r e d and e j e c t e d e l e c t r o n s , and we will

t h e r e f o r e not c o n s i d e r the p r o b l e m of i o n i z a t i o n at t h i s s t a g e . A f u r t h e r
m o d i f i c a t i o n of E q . (1) i s r e q u i r e d if the t a r g e t i s an ion. In t h i s c a s e
l o g a r i t h m i c p h a s e f a c t o r s m u s t be included in the e x p o n e n t s to allow f o r
the l o n g - r a n g e d i s t o r t i o n due to the Coulomb f i e l d . T h i s , h o w e v e r ,
i n t r o d u c e s no e s s e n t i a l c o m p l i c a t i o n and we t h e r e f o r e o m i t t h e s e t e r m s
at the m o m e n t in o r d e r to m a i n t a i n f o r m a l s i m p l i c i t y .
Of c o u r s e s c a t t e r i n g i s only p o s s i b l e into t h o s e s t a t e s t h a t a r e e n e r -
g e t i c a l l y allowed having k 2 s 0. The r e m a i n i n g s t a t e s with k j < 0 can
only e x i s t v i r t u a l l y f o r a s h o r t t i m e d u r i n g the c o l l i s i o n and will t h u s not
c o n t r i b u t e to the a s y m p t o t i c f o r m in E q . (1). T h i s i s c l e a r s i n c e they will
contain d e c a y i n g e x p o n e n t i a l . f a c t o r s in (1). H o w e v e r , such s t a t e s m a y
p l a y an i m p o r t a n t r o l e d u r i n g the collision p r o c e s s itself and can in c e r t a i n
c i r c u m s t a n c e s give r i s e to r e s o n a n c e s .
We a r e now in a p o s i t i o n to define the c r o s s - s e c t i o n f o r a t r a n s i t i o n
f r o m s t a t e i to s t a t e j with the s c a t t e r e d e l e c t r o n spin m a g n e t i c quantum
n u m b e r changing f r o m m ; to m j . The d i f f e r e n t i a l c r o s s - s e c t i o n i s
а . . ( б , ф ) = £ i | f j t (в,ф) I2 (3)
Í
and t h e t o t a l c r o s s - s e c t i o n i s obtained by i n t e g r a t i n g o v e r all a n g l e s of the

s c a t t e r e d e l e c t r o n and s u m m i n g over all f i n a l s t a t e s .
1.2. P a r t i a l wave a n a l y s i s
At low i n c i d e n t e l e c t r o n e n e r g i e s , w h e r e the e l e c t r o n - a t o m i n t e r a c t i o n
i s p a r t i c u l a r l y s t r o n g , it i s convenient, both f r o m a t h e o r e t i c a l and f r o m
an e x p e r i m e n t a l point of view, to a n a l y s e fjj (в, ф) in t e r m s of p a r t i a l w a v e s .
F o r light a t o m i c s y s t e m s such a s t h o s e in the f i r s t r o w of the p e r i o d i c
t a b l e the s p i n - d e p e n d e n t t e r m s in the H a m i l t o n i a n a r e s m a l l and can u s u a l l y
be n e g l e c t e d . In t h i s c a s e L, the total o r b i t a l a n g u l a r m o m e n t u m , and S,
the t o t a l spin a n g u l a r m o m e n t u m , and t h e i r z - c o m p o n e n t s a s well a s the
p a r i t y 7Г a r e s e p a r a t e l y c o n s e r v e d d u r i n g the c o l l i s i o n . It i s convenient
t h e n , to c h o o s e a r e p r e s e n t a t i o n in which t h e s e q u a n t i t i e s a r e diagonal.
L a t e r we s h a l l extend o u r d i s c u s s i o n to h e a v i e r a t o m s and in t h i s c a s e we
s h a l l find that only J , the t o t a l a n g u l a r m o m e n t u m , i t s z - c o m p o n e n t and
7Г a r e c o n s e r v e d .
We c a r r y out an a n a l y s i s s i m i l a r to that f i r s t u s e d by B l a t t and
B i e d e n h a r n (1952) in d i s c u s s i n g the t h e o r y of n u c l e a r c o l l i s i o n s . We
define the c h a n n e l in which the collision o c c u r s by the c o m p l e t e s e t of
quantum n u m b e r s
Г = « j L j S j jPj S L M s M l t t (4)
w h e r e <*j L j S ; s p e c i f y the a t o m i c state and i i i s the o r b i t a l a n g u l a r m o m e n -

t u m of the s c a t t e r e d e l e c t r o n . During a c o l l i s i o n OjLj S ; and i j m a y change
but we have s e e n that L S M L M s and 7R a r e c o n s e r v e d . F r o m the u s u a l
a n g u l a r m o m e n t u m addition r u l e s the t r i a n g u l a r r e l a t i o n s
IAEA-SMR-12/17,19 527
| Ц - jřJ š L + ^
(5)
I Sj - i I s S š S ^ I
m u s t be s a t i s f i e d . A s s o c i a t e d with e a c h c h a n n e l we can define a c h a n n e l

function
® Í ( X Л . . . xN ř N + 1 aN+1 ) = ^ C L . ( L M L ; ML. m , . )
Мц,Ш{.
Mc , m-1
m
ř< . rrv
X C S i | ( S M s ; Ms. m s ) ^ ( x , . . . x N ) Y ť . 1 (r N + 1 ) x f 1 (aN + 1 ) (6)
w h e r e x; = r ; i s the s p a c e and spin c o - o r d i n a t e of the i - t h e l e c t r o n and

we a s s u m e t h a t the a t o m c o n t a i n s N e l e c t r o n s . In t h i s e q u a t i o n we h a v e
i n t r o d u c e d C l e b s c h - G o r d o n c o e f f i c i e n t s (see E d m o n d s , 1957) in coupling
the a n g u l a r m o m e n t a of the a t o m and the s c a t t e r e d e l e c t r o n .
We now p r o c e e d by e x p a n d i n g the t o t a l wave f u n c t i o n in E q . (1) in t e r m s
of t h e s e c h a n n e l f u n c t i o n s ,
N+L
k=l j
w h e r e N; i s a n o r m a l i z a t i o n f a c t o r and the s u m o v e r к e n s u r e s t h a t Ф i s
a n t i s y m m e t r i c in the c o - o r d i n a t e s of a l l N + l e l e c t r o n s , as r e q u i r e d by
the P a u l i p r i n c i p l e . The r a d i a l f u n c t i o n s и ] Ч (г), which d e s c r i b e the m o t i o n
of the s c a t t e r e d e l e c t r o n , w i l l be shown l a t e r to be s o l u t i o n s of a s y s t e m of
coupled i n t e g r o - d i f f e r e n t i a l e q u a t i o n s s a t i s f y i n g the b o u n d a r y c o n d i t i o n s
U j i (0) = 0
u 1 (r) ~ k"* (sin ft 6.. + c o s а К й ); k? г 0 (8)

J r —» oo J J Jl J Jl J
Uj:(r) ~ 0 ( r " 2 ) ; k? < 0

J* Г —> ос J
w h e r e 0j = k^r - } JjW f o r n e u t r a l a t o m s . T h i s equation d e f i n e s the r e a l

and s y m m e t r i c K - m a t r i x which h a s the d i m e n s i o n of the n u m b e r of open
c h a n n e l s ( i . e . c h a n n e l s with k 2 S 0). We can d e f i n e a u n i t a r y and s y m m e t r i c
S - m a t r i x by t a k i n g l i n e a r c o m b i n a t i o n s of the s o l u t i o n s defined by E q . (8).
We w r i t e t h e s e t r a n s f o r m e d s o l u t i o n s , u s i n g the s a m e notation и-ц(г) f o r
t h e s e new r a d i a l f u n c t i o n s , a s
Uji (0) = 0
r (e
v > "ieíóii - е
"Ч>= k
b ° <9>
Uji(r) ^0(r"2); k? < 0

528 BURKE
which i m p l i e s a d i f f e r e n t n o r m a l i z a t i o n N ; in E q . (7). It f o l l o w s that

К and S a r e r e l a t e d by the m a t r i x equation
+
s=! (io)
1 - iK
In o r d e r to obtain an e x p r e s s i o n for the s c a t t e r i n g a m p l i t u d e in t e r m s of

the S - m a t r i x we f i r s t expand the incident plane wave t e r m in E q . (1) u s i n g
the w e l l - k n o w n r e s u l t
ikz
e = ^ (2j? + l) ^ £ ( к г ) Р { ( c o s ö ) (11)
£=0
w h e r e j f (kr)^ ~ ^ ( k r ) _ 1 s i n ( k r - \ $ к). We find that
I г •
ф^Тех p ( i k j Z N + 1) - — ) a , ( L M L ; M O)
X C s i ( S M s ; Ms m . ) i í í ( 2 í . + 1 f $ . ( x r . . x N f ^ a N + 1 )(e" i 0 i - e i 6 i ) (12)
We now e q u a t e the c o e f f i c i e n t of the ingoing wave in E q s (7) and (12), u s i n g

the b o u n d a r y c o n d i t i o n s (9). T h i s d e f i n e s the n o r m a l i z a t i o n f a c t o r Nj in
E q . (7). If we now w r i t e in analogy with E q . (1)
(13)
w h e r e Ф.I inc
. is d e f i n e d by
J (12), then we find t h a t
* "
„
1 scatt
~ ) ^ CLÍ ( L Ml , ; M, 0) C 4 . (SM • M m, )
rN + 1-*«> kXk г r N + J 4% ' Ч V s- Si i'
a l s
ii i
Х ^ Щ + l ) i ® j ( X l . . . x N r N + 1 a N + 1 ) (6 П - S ^ e ^ ' (14)
E x p a n d i n g <řj in t e r m s of the a t o m i c s t a t e s we find in a g r e e m e n t with

E q . (1) t h a t
eXP(ikJ
Ф. „ - У ф (X . . . X J K T' f, ( ř m l ) 'rN + l)
(15)
r
i scatt r £_, * i N' Ji N+l' N + l
a L S
j j j
м м т
ь 5] )
IAEA-SMR-12/17,19 529
w h e r e the s c a t t e r i n g a m p l i t u d e
i
% (î) = - 1 ( i n r ) I i V i i ( 2 i i + 1)* C 4 i . (LMl;M40)

1 J
" LS f j ü j
X Csj(SMs; M ^ m J C L . (L M L ; M t m , ) C s . , ( S M s ; M m j )
f J J J J Л J
x
(Su - v Y;'. í j '(ř) de)
This scattering amplitude d e s c r i b e s a transition between states defined

by the q u a n t u m n u m b e r s
a , L j S j M , Mc m. and a . L . S . M ,b M- m . (17)
i i i J J ] j J
If the spin d i r e c t i o n s a f t e r s c a t t e r i n g a r e not o b s e r v e d and the incident

e l e c t r o n b e a m and t h e a t o m i c t a r g e t a r e u n p o l a r i z e d , then we m u s t a v e r a g e
o v e r the i n i t i a l spin d i r e c t i o n s and s u m o v e r the f i n a l spin d i r e c t i o n s . A f t e r
i n t e g r a t i n g o v e r all a n g l e s we find that the t o t a l c r o s s - s e c t i o n f o r a t r a n s i -
tion f r o m s t a t e Oj L j S j to s t a t e L.S^ i s
- V ( 2 L + 1 ) ( 2 S + 1 ) i ,2
|S 1 (18)
" kf L 2 ( 2 L j + 1) (2 Sj + 1) ii " S
LS%Cj
F o r an ion the s c a t t e r i n g a m p l i t u d e c o n t a i n s an a d d i t i o n a l t e r m when i = j

a r i s i n g f r o m the l o n g - r a n g e Coulomb p o t e n t i a l .
In s o m e a p p l i c a t i o n s it i s u s e f u l to i n t r o d u c e a c o l l i s i o n s t r e n g t h
d e f i n e d by
Q ( i j ) = к * ( 2 Ц + 1)(2S. + l ) a 4 (19)
It i s c l e a r f r o m the d e f i n i t i o n that S?(ij) = Г2(j i).
'1.3. Fine-structure transitions

In m a n y c a s e s it is of i n t e r e s t to know the c r o s s - s e c t i o n s f o r t r a n s i -
t i o n s involving the f i n e - s t r u c t u r e l e v e l s of an a t o m ' o r of an ion. In p a r t i -
c u l a r t h i s i s t h e c a s e f o r s y s t e m s with high n u c l e a r c h a r g e Z . The r e p r e -
s e n t a t i o n u s e d in the p r e v i o u s s e c t i o n i s not a p p r o p r i a t e and we have to
t r a n s f o r m f r o m t h e coupling s c h e m e defined by
(S; \ ) S ( L j í j ) L J M j (20)
to the coupling s c h e m e d e f i n e d by
(SjLj) J i d i j ) J i J M, (21)
530 BURKE
T h i s can be a c h i e v e d u s i n g the Wigner 9 - j c o e f f i c i e n t d e f i n e d by E d m o n d s

(1957). We find t h a t
((SjLj) X , ( i i j ) j , , j | ( S j i ) S , ( L . i . ) L , J)
Si Ц J^
t (2 J j + 1) (2j + 1) (2S + 1) (2L + 1) ] - i2 4
(22)
'i 3i
S L J
If the s p i n - o r b i t i n t e r a c t i o n is s m a l l we can apply t h i s t r a n s f o r m a t i o n to

the S - m a t r i x defined in the p r e v i o u s s e c t i o n giving the S - m a t r i x in the
new r e p r e s e n t a t i o n a s
S(o.
1
1 L.S.J,
1 1 1i lJl
i . J ,' o 3. L .JSJ J.] i .JjJ .j J )
4 Ji\ 1 L
Jj.) S(<*. L . S . Í . S L , a.L.S.j?. S L) A I 2 jj |(23)
'i i i i i i j j j j
L J / \< S L
w h e r e the t r a n s f o r m a t i o n m a t r i x A i s d e f i n e d by t h e r i g h t - h a n d side of
Eq. (22). If one of the two t e r m s involved in the t r a n s i t i o n c o n t a i n s one
f i n e - s t r u c t u r e l e v e l , then the e x p r e s s i o n f o r the c o l l i s i o n s t r e n g t h in the
t r a n s f o r m e d r e p r e s e n t a t i o n i s p a r t i c u l a r l y s i m p l e . We h a v e
2 JJ + 1
ЖЕ,ЦБ,, EJLJSJJJ) = ( 2 S J + 1) ( 2 L J + 1 ) NÎ^S,, ORJLJSJ) (24)
if L j = 0 o r if Sj = 0.
2. T H E C L O S E - C O U P L I N G APPROXIMATION AND
SOME R E C E N T D E V E L O P M E N T S
2.1. Intr o duction
In o r d e r to obtain e x p l i c i t e q u a t i o n s s a t i s f i e d by the r a d i a l f u n c t i o n s
Ujj (r), i n t r o d u c e d in the p r e v i o u s s e c t i o n , we have to a p p r o x i m a t e our
t o t a l wave f u n c t i o n in s o m e way. The c l o s e - c o u p l i n g a p p r o x i m a t i o n
a s s u m e s t h a t only c h a n n e l s c o r r e s p o n d i n g to a few l o w - l y i n g s t a t e s of
the a t o m a r e i m p o r t a n t and that we can n e g l e c t the p r o b a b i l i t y t h a t the
a t o m will m a k e t r a n s i t i o n s to all other s t a t e s including the continuum.
If we a s s u m e t h a t n c h a n n e l s a r e i m p o r t a n t then the t o t a l wave f u n c t i o n
in the c l o s e - c o u p l i n g a p p r o x i m a t i o n i s , in a n a l o g y with E q . (7),
IAEA-SMR-12/17,19 531
N+l
i
Ф. = (N + l ) - * X ( - l ) N + 1 " k ^ (Xj . . . Xi(-lxk+l' . • XN+1 £ k a k ' r k l u j i ( r k ) (25)
k=1 j=l
T h i s a p p r o x i m a t i o n w a s f i r s t i n t r o d u c e d by M a s s e y and Möhr (1932) sind

in i t s m o d e r n f o r m with the i n c l u s i o n of e l e c t r o n a n t i s y m m e t r i z a t i o n , by
Seaton (1953).
T h i s a p p r o x i m a t i o n h a s b e e n u s e d to study a l a r g e n u m b e r of t r a n s i -
t i o n s . We will s e e that it i s v e r y s a t i s f a c t o r y when the c h a n n e l s included
in E q . (25) a r e well i s o l a t e d in e n e r g y f r o m the n e g l e c t e d c h a n n e l s , but it
m a y give p o o r r e s u l t s o t h e r w i s e . S e v e r a l a t t e m p t s have b e e n m a d e to
i m p r o v e the a p p r o x i m a t i o n to allow f o r the o m i t t e d c h a n n e l s and we will
d i s c u s s t h e s e l a t e r in s e c t i o n 2.3.
2.2. The c l o s e - c o u p l i n g e q u a t i o n s
The c l o s e - c o u p l i n g e q u a t i o n s can be d e r i v e d f r o m K o h n ' s v a r i a t i o n a l

p r i n c i p l e (Hulthèn, 1944 and Kohn, 1948). We d e f i n e an i n t e g r a l
ф
hi = J * (H-E)fjdx1....dxN +1 (26)
w h e r e the i n t e g r a t i o n i s c a r r i e d out o v e r the s p a c e and spin c o - o r d i n a t e s

of all N + 1 e l e c t r o n s and the H a m i l t o n i a n
N+l N+l
1 J
i=l i> j=1
in a t o m i c u n i t s . We now c o n s i d e r s m a l l v a r i a t i o n s of the f u n c t i o n s Ujj (r)
about t h e i r e x a c t s o l u t i o n s d e f i n e d by the b o u n d a r y c o n d i t i o n s (8), such that
б Uji(0) = 0
б u f i (r) - k* c o s fl.fi K.. 1; kf š 0 (28)

J j —> oo i * J J
б u - (r ) - 0(r" 2 ); к? < 0
" Г -*• oo J
It follows t h a t the following f u n c t i o n a l i s s t a t i o n a r y
6(Iy - 1 K y ) = 0 (29)
p r o v i d e d the Uj;(r) s a t i s f y the i n t e g r o - d i f f e r e n t i a l e q u a t i o n s

П «о
l ( 1} r 2 r
( Ž - ' y + V > = I ( v > +/Kjk(r,r.)uki(r.)dr')
k=1 0
(30)
532 BURKE
H e r e the p o t e n t i a l i s defined by
N
V
jk(rN + l> = < $ j < x l - • -xnÎn+1ctN+1 ) ( / ZT T~)®k( X
r- x
NlN + l a
N + l)>
• i N +1 N +1
1-1
(31)
and the e x c h a n g e k e r n e l i s d e f i n e d by
r u
/ % ( % +!. N) ki(rN>drN =
" N
< $
j( x
i - • ^ n Î n + I^n+I)
0
X (H-E)$k(xr,.xN.1xN+15iaN)r-1Uki(rN)> (32)
w h e r e in both (31) and (32) the i n t e g r a t i o n s a r e c a r r i e d out o v e r all c o -

o r d i n a t e s e x c e p t o v e r the r a d i a l c o - o r d i n a t e r N + 1 .
T h e e v a l u a t i o n of t h e d i r e c t potential and e x c h a n g e k e r n e l s can be
v e r y t e d i o u s e x c e p t f o r the s i m p l e s t a t o m i c s y s t e m s such a s H and He.
In the c a s e of a t o m i c h y d r o g e n the e q u a t i o n s have been w r i t t e n down
e x p l i c i t l y by P e r c i v a l and Seaton (1957). It i s now u s u a l to c a r r y out
the a l g e b r a i c r e d u c t i o n by c o m p u t e r a s d i s c u s s e d by s e v e r a l a u t h o r s
( e . g . Smith and M o r g a n , 1968, Burke et al. , 1971, and E i s s n e r and
Seaton, 1972).
One i m p o r t a n t f e a t u r e that d i s t i n g u i s h e s e l e c t r o n a t o m s c a t t e r i n g
f r o m the c o r r e s p o n d i n g p r o b l e m in n u c l e a r p h y s i c s i s the long r a n g e
n a t u r e of the d i r e c t p o t e n t i a l . It follows f r o m Eq. (31) that
M
6 +
V ^ - ^ T ^ jk Ха*г"Х_1 f33)
Х=1
The f i r s t t e r m i s the Coulomb potential. In addition we s e e that t h e r e
a r e o f f - d i a g o n a l p o t e n t i a l s b e h a v i n g l i k e r" n . T h o s e with n = 2 couple s t a t e s b e t w e e n
which e l e c t r i c dipole t r a n s i t i o n s a r e allowed and l e a d in s e c o n d o r d e r to
the p o l a r i z a t i o n of the t a r g e t a t o m . On the o t h e r hand the exchange k e r n e l
v a n i s h e s e x p o n e n t i a l l y at l a r g e d i s t a n c e s .
The solution of the c l o s e - c o u p l i n g e q u a t i o n s (30) s u b j e c t to the b o u n d a r y
c o n d i t i o n s (8) can a l s o only be c a r r i e d out n u m e r i c a l l y . V a r i o u s t e c h -
n i q u e s u s e d in t h e i r s o l u t i o n have r e c e n t l y b e e n d i s c u s s e d by B u r k e and
Seaton (1971).
2.3.. The i n c l u s i o n of h i g h e r c h a n n e l s
It i s c l e a r t h a t it i s n e i t h e r p h y s i c a l l y m e a n i n g f u l , n o r indeed n u m e r i -
c a l l y f e a s i b l e , to include m o r e than a few c h a n n e l s in the c l o s e - c o u p l i n g
e x p a n s i o n (usually n l i e s b e t w e e n 2 and 10 s e l d o m e x c e e d s 20). T h i s i s
b e c a u s e the w e l l - k n o w n s p e c t r u m of an a t o m , with an infinite n u m b e r of
bound s t a t e s c o n v e r g i n g onto the f i r s t continuum t h r e s h o l d , m e a n s t h a t an
infinite n u m b e r of c h a n n e l s would have to be included b e f o r e the continuum
could be c o n s i d e r e d . H o w e v e r , in c e r t a i n c i r c u m s t a n c e s the continuum
IAEA-SMR-12/17,19 533
can be s i g n i f i c a n t . F o r e x a m p l e , in the o s c i l l a t o r s t r e n g t h s u m r u l e f o r
the a t o m i c p o l a r i z a b i l i t y
(34)
an i m p o r t a n t c o n t r i b u t i o n f o r m a n y a t o m i c s y s t e m s c o m e s f r o m the continuum.
The o m i s s i o n of the continuum s t a t e s f r o m the c l o s e coupling e x p a n s i o n
m e a n s t h a t only p a r t of a i s included, t h r o u g h the X = 1 t e r m s in (33), and
q u a n t i t i e s which depend s e n s i t i v e l y on the l o n g - r a n g e p o t e n t i a l , s u c h a s the
s m a l l - a n g l e e l a s t i c - s c a t t e r i n g c r o s s - s e c t i o n , will be in e r r o r .
It i s convenient to d i s c u s s the e f f e c t of c h a n n e l s o m i t t e d f r o m the c l o s e
coupling e x p a n s i o n u s i n g the p r o j e c t i o n o p e r a t o r f o r m a l i s m of F e s h b a c h
(1962). We define P a s the o p e r a t o r which p r o j e c t s onto the c h a n n e l s included
in the c l o s e - c o u p l i n g e x p a n s i o n and Q a s the o p e r a t o r which p r o j e c t s onto
the r e m a i n i n g o m i t t e d c h a n n e l s . Then
P + Q = 1
P 2 = P; Q2 = Q (35)
PQ = QP = 0
The S c h r ö d i n g e r equation
(H - Е)Ф = 0 (36)
can then be f o r m a l l y r e w r i t t e n a s
P (H - E) (P + Q)<ř = 0
(37)
Q(H - E) (P + Q)Ф = 0
We can solve the s e c o n d of t h e s e e q u a t i o n s f o r Q ^ giving
1
Q^ = - Q QHPi' (38)
Q (H - E) Q
and s u b s t i t u t e into the f i r s t e q u a t i o n s giving
(39)
T h i s i s of c o u r s e e q u i v a l e n t to our o r i g i n a l e q u a t i o n (36). The c l o s e -

coupling e q u a t i o n s in t h i s notation a r e
534 BURKE
P (H - E ) РФ P = О (40)
It i s c l e a r that the a d d i t i o n a l " o p t i c a l " p o t e n t i a l
v
°pt =
- P H
% ( H ! E ) Q Q H P
<41)
a l l o w s f o r the e f f e c t of t h e s e o m i t t e d c h a n n e l s . Below the f i r s t t h r e s h o l d

o m i t t e d f r o m t h e c l o s e - c o u p l i n g e x p a n s i o n V opt i s r e a l , and indeed can be
shown to be n e g a t i v e d e f i n i t e c o r r e s p o n d i n g to p u r e a t t r a c t i o n ( G a i l i t i s , 1964,
Hahn et al. , 1 9 6 4 a , b and McKinley and M a c e k , 1964). Above t h i s t h r e s h o l d
it b e c o m e s c o m p l e x giving r i s e to l o s s of flux into the o m i t t e d c h a n n e l s .
A n u m b e r of m e t h o d s have been p r o p o s e d which m a k e s o m e a l l o w a n c e
for Vopt. These are:
(a) Cor r e lation-fun£tion_expan_sion _method_
In t h i s a p p r o a c h we expand
c.X. (42)
w h e r e the Xj a r e s q u a r e i n t e g r a b l e f u n c t i o n s in the Q - s p a c e which involve

the c o - o r d i n a t e s of all (N + l ) e l e c t r o n s . T h i s c o r r e s p o n d s to w r i t i n g
^ P m V O q H P (43)
í Ej - E
It i s c l e a r t h a t t h i s a p p r o x i m a t i o n f o r Vopt i s r e a l and t h u s t h i s a p p r o a c h
i s only s a t i s f a c t o r y below t h e f i r s t continuum t h r e s h o l d of QHQ. H o w e v e r ,
in t h i s e n e r g y r e g i o n it h a s b e e n v e r y s u c c e s s f u l p a r t i c u l a r l y f o r e" - H
s c a t t e r i n g w h e r e H y l l e r a a s t e r m s can be u s e d to r e p r e s e n t the e l e c t r o n -
e l e c t r o n c o r r e l a t i o n (Burke and T a y l o r , 1966, and T a y l o r and B u r k e , 1967).
We note that the h i e r a r c h y of e q u a t i o n s d i s c u s s e d by N e s b e t (1967) i n v o l v e s
the i n c l u s i o n of t e r m s s i m i l a r to Eq. (42).
(b) P s _ f 4 d o - s t a t e _ e x p a n s i o n me_thod_
Although e x p a n s i o n (42) can be c a r r i e d out in t e r m s of a c o m p l e t e s e t

of f u n c t i o n s it i s not a l w a y s c l e a r how f a s t it will c o n v e r g e in p r a c t i c e .
If, h o w e v e r , we a r e j u s t i n t e r e s t e d in including the l o n g - r a n g e p o t e n t i a l ,
a s u m r u l e can be u s e d which will give the c o r r e c t f o r m of the o p t i c a l
p o t e n t i a l in t h i s l i m i t . T h i s w a s f i r s t pointed out by D a m b u r g and K a r u l e
(1967).
To s e e t h i s we f i r s t w r i t e Eq. (34) a s
\Г<ф01м1|ф1><ф;1м1|Фо> (44)
a =2
Z_i E. • "EJon
IAEA-SMR-12/17,19 535
w h e r e Mj = ^ z. i s the u s u a l dipole length o p e r a t o r and ф0 and ф. a r e ,

i
r e s p e c t i v e l y , the a t o m i c ground s t a t e and the c o m p l e t e set of a t o m i c
i n t e r m e d i a t e s t a t e s . In t h i s f o r m we s e e f r o m (41), t h a t (44) i s j u s t
the l i m i t of r 4 V opt a s r -» со.
We now i n t r o d u c e a p s e u d o - s t a t e фр which i s the solution of
(Н-Е0)фр = M ^ o (45)
It then f o l l o w s that Eq. (44) can be r e p l a c e d by
2<Ф0|М!|фр>
E E
p - o
w h e r e ф р i s n o r m a l i z e d to unity and w h e r e E p = <[ ф р | н | фр )>. In the c a s e of

e l a s t i c s c a t t e r i n g we can now r e p l a c e the c l o s e - c o u p l i n g e x p a n s i o n (25) by
:
jtf Ф 0 г _ 1 и ( г ) + ^ ® p i r" 1 v i (r) (47)
where i s the a n t i s y m m e t r i z a t i o n o p e r a t o r , Ф0 i s the c h a n n e l function

c o r r e s p o n d i n g to ф0 , and <řpi a r e the c h a n n e l f u n c t i o n s c o r r e s p o n d i n g to
ф р . We then obtain, in the u s u a l way, coupled i n t e g r o - d i f f e r e n t i a l
e q u a t i o n s f o r the r a d i a l f u n c t i o n s u ( r ) and VJ(r). The c o r r e s p o n d i n g
solution c o n t a i n s the f u l l a t o m i c p o l a r i z a b i l i t y .
We note that the solution of (45) can be c a r r i e d out v a r i a t i o n a l l y ,
h o w e v e r , in the c a s e of a t o m i c h y d r o g e n it h a s an e x a c t solution whose
radial part is
r ) =
V (fig)2 (ir3+r2)e"r (48)
If we a r e i n t e r e s t e d in i n e l a s t i c s c a t t e r i n g , p s e u d o - s t a t e s can be c h o s e n
which will s u m any r e q u i r e d c o m p o n e n t of the l o n g - r a n g e p o t e n t i a l
( D a m b u r g , 1972). A f u r t h e r f e a t u r e of i m p o r t a n c e i s t h a t the c o r r e s p o n d i n g
r e p r e s e n t a t i o n of the o p t i c a l p o t e n t i a l b e c o m e s c o m p l e x above the e n e r g y
E p . It m a y t h e r e f o r e be p o s s i b l e to choose, the p s e u d o - s t a t e s to give the
c o r r e c t i n e l a s t i c i t y (Burke and Webb, 1970).
(c) P o l a £ i z e d - o r b i t a . l _m£thod_
T e m k i n (1959), v e r y m u c h e a r l i e r , i n t r o d u c e d a m e t h o d f o r e l a s t i c
s c a t t e r i n g which can be s e e n to be c l o s e l y a n a l o g o u s to the p s e u d o - s t a t e
m e t h o d d i s c u s s e d above. R a t h e r than i n t r o d u c e a n u m b e r of u n d e t e r m i n e d
f u n c t i o n s a s in Eq. (4 7) he w r o t e
Ф= ^ [ Ф 0 + e г" 2 Ф р ] r _ 1 u (r) (49)

536 BURKE
w h e r e e i s a cut-off f a c t o r which o m i t s the s e c o n d t e r m when the incident

e l e c t r o n c o - o r d i n a t e is l e s s than the a t o m i c c o - o r d i n a t e s . Only one
f u n c t i o n u ( r ) need now be d e t e r m i n e d and the m e t h o d t h u s g a i n s in n u m e r i c a l
s i m p l i c i t y a l b e i t at the e x p e n s e of a c c u r a c y .
T h i s a p p r o a c h y i e l d s a p u r e l y r e a l e q u i v a l e n t o p t i c a l p o t e n t i a l and
t h u s h a s no p o s s i b i l i t y of r e p r e s e n t i n g i n e l a s t i c e f f e c t s . H o w e v e r , t h e
m e t h o d h a s b e e n extended to i n e l a s t i c s c a t t e r i n g by F e u t r i e r et al. (1971)
by i n c l u d i n g a p o l a r i z e d - o r b i t a l s t a t e фр in e a c h c h a n n e l .
(d) Se£ondôrderj3êjitml_m_etho_d
In r e c e n t work by B r a n s d e n and C o l e m a n (1972) the o p t i c a l p o t e n t i a l

h a s b e e n e v a l u a t e d by r e p l a c i n g the i n t e r m e d i a t e s t a t e s by p l a n e - w a v e
s t a t e s and then e v a l u a t i n g the s u m m a t i o n by a c l o s u r e a p p r o x i m a t i o n which
can be c h o s e n to give the c o r r e c t l o n g - r a n g e i n t e r a c t i o n . T h i s m e t h o d
c l e a r l y h a s s o m e p o i n t s of c o m p a r i s o n with the p s e u d o - s t a t e e x p a n s i o n
method discussed earlier.
3. LOW-ENERGY E L E C T R O N - A T O M SCATTERING
3.1. Introduction
In t h i s p a r t we r e v i e w v e r y b r i e f l y s o m e r e c e n t e x p e r i m e n t a l and
t h e o r e t i c a l r e s u l t s in l o w - e n e r g y e l e c t r o n - a t o m s c a t t e r i n g . Our choice
m u s t n e c e s s a r i l y be s e l e c t i v e in view of the v a s t amount of d a t a now a v a i l -
able. A s a r e s u l t we will a t t e m p t to look at e x a m p l e s which i l l u s t r a t e
f e a t u r e s which m a y be e x p e c t e d to have r a t h e r g e n e r a l i n t e r e s t . We will
s t a r t with e - H s c a t t e r i n g which i s i m p o r t a n t both b e c a u s e it p r o v i d e s a
m o d e l f o r m o r e c o m p l e x a t o m i c s y s t e m s and also b e c a u s e a t o m i c h y d r o g e n
i s one of the c o m m o n e s t c o n s t i t u e n t s in the U n i v e r s e . Next we will b r i e f l y
r e v i e w e" - He + s c a t t e r i n g which o c c u p i e s the s a m e p o s i t i o n v i s - à - v i s
e l e c t r o n - i o n c o l l i s i o n s a s e" - H s c a t t e r i n g d o e s v i s - à - v i s e l e c t r o n - a t o m
c o l l i s i o n s . F o r both of t h e s e s y s t e m s r e s o n a n c e s p l a y an i m p o r t a n t p a r t
in the c o l l i s i o n p r o c e s s and we will spend s o m e t i m e d i s c u s s i n g how t h e s e
a r i s e . Next we m o v e onto the c o l l i s i o n of e l e c t r o n s with the a l k a l i m e t a l
a t o m s . It i s h e r e that both e x p e r i m e n t and t h e o r y a r e e x p e c t e d to give the
m o s t r e l i a b l e r e s u l t s and s o m e of the m o s t d e t a i l e d c o m p a r i s o n s involving
s p i n - p o l a r i z e d e l e c t r o n s and a t o m s have b e e n m a d e f o r such s y s t e m s .
F i n a l l y , we look at the s c a t t e r i n g of e l e c t r o n s by a t o m s and ions with np 4
o u t e r s h e l l s . E x p e r i m e n t s h e r e a r e d i f f i c u l t if not i m p o s s i b l e at p r e s e n t ,
yet t r a n s i t i o n s involving t h e s e s y s t e m s a r e of f u n d a m e n t a l i m p o r t a n c e in
many astrophysical applications.
3.2. E l e c t r o n s c a t t e r i n g by a t o m i c h y d r o g e n
(a) Elastic_s£atte_ring_
H e r e t h e m o s t a c c u r a t e c a l c u l a t i o n s below the f i r s t e x c i t a t i o n t h r e s h o l d
have b e e n c a r r i e d out by S c h w a r t z (1961) f o r S - w a v e s c a t t e r i n g and by
IAEA-SMR-12/17,19 537
A r m s t e a d (1968) f o r P - w a v e . s c a t t e r i n g . T h e y u s e d t r i a l f u n c t i o n s i n c l u d i n g
up to 50 H y l l e r a a s - t y p e t e r m s in the Kohn v a r i a t i o n a l p r i n c i p l e E q . (29).
S i n c e t h e y did not i n c l u d e the 2s and 2p s t a t e s e x p l i c i t l y , t h e c a l c u l a t i o n
of S c h w a r t z and A r m s t e a d b e c o m e s l e s s a c c u r a t e a s the f i r s t e x c i t a t i o n
t h r e s h o l d i s a p p r o a c h e d . In t h i s c a s e t h e m e t h o d u s e d by B u r k e and T a y l o r
(1966) w h e r e the t o t a l wave f u n c t i o n i s e x p a n d e d in t e r m s of t h e I s 2s and
2p a t o m i c e i g e n s t a t e s and a n u m b e r of H y l l e r a a s t y p e c o r r e l a t i o n f u n c t i o n s
is m o r e satisfactory.
J u s t b e l o w t h e n = 2 t h r e s h o l d , at 9.56 eV, a 1 S r e s o n a n c e i s found with
a width of about 0.0475 e V . T h i s r e s o n a n c e c o r r e s p o n d s to a bound s t a t e of
QHQ w h e r e Q i s c h o s e n to p r o j e c t onto a l l e x c i t e d s t a t e s of the t a r g e t .
Defining
QHQ 6j = ejöj (50)
t h e n the o p t i c a l p o t e n t i a l of E q . (41) b e c o m e s
V (51)
°Pt - E
i
w h e r e t h e s u m i n c l u d e s an i n t e g r a t i o n o v e r t h e c o n t i n u o u s s p e c t r u m of
QHQ. F e s h b a c h (1962) s h o w e d t h a t a p o l e in V opt g i v e s r i s e to a r e s o n a n c e
in t h e s o l u t i o n of E q . (39) w h e r e the width of the r e s o n a n c e i s
Ц = 2v | < е ^ Н Р \ Р . + > I 2 (52)
H e r e РФ* i s the a p p r o p r i a t e l y n o r m a l i z e d s o l u t i o n of E q . (3 9) o m i t t i n g the

i - t h pole f r o m Vopt.
G a i l i t i s and D a m b u r g (1963) s h o w e d t h a t the m e c h a n i s m which c a u s e s
t h e b i n d i n g of the s t a t e s Sj in e" - H s c a t t e r i n g i s the l o n g - r a n g e d e g e n e r a t e
d i p o l e i n t e r a c t i o n . T h i s r e s u l t s in an i n f i n i t e s e r i e s of r e s o n a n c e s b e l o w
e a c h e x c i t e d t h r e s h o l d and in a d d i t i o n m o d i f i e s t h e t h r e s h o l d b e h a v i o u r
of the e x c i t a t i o n c r o s s - s e c t i o n s . F i g u r e 1 s h o w s a m e a s u r e m e n t of the
e l a s t i c s c a t t e r i n g c r o s s - s e c t i o n c l o s e to 90° by McGowan et a l . (1965).
T h r e e r e s o n a n c e s a r e a p p a r e n t , a 1 S r e s o n a n c e at 9.56 eV, a P r e s o n a n c e
at 9.74 e V and a 1 D r e s o n a n c e at 10.125 e V . O t h e r t h e o r e t i c a l l y p r e d i c t e d
r e s o n a n c e s a r e too n a r r o w to be s e e n in t h i s e x p e r i m e n t .
(b) l_s_- 2 s and _ls_- 2p _excit_ation
We show in F i g . 2 s e v e r a l c a l c u l a t i o n s of t h e I s - 2s e x c i t a t i o n c r o s s -
s e c t i o n c l o s e to t h r e s h o l d . T h e y a r e t h e I s - 2s - 2p c l o s e - c o u p l i n g a p p r o x i -
m a t i o n ( B u r k e et al. , 1963), the I s - 2s - 2p - 3s - 3p - 3d c l o s e - c o u p l i n g
a p p r o x i m a t i o n ( B u r k e et a l . , 1967) and t h e I s - 2s - 2p - p l u s - t w e n t y
c o r r e l a t i o n - f u n c t i o n a p p r o x i m a t i o n ( T a y l o r and B u r k e , 1967).
We s e e t h a t a l l t h r e e a p p r o x i m a t i o n s a r e in good a g r e e m e n t b e l o w the
n = 3 t h r e s h o l d . In t h i s r e g i o n t h e y all h a v e the c o r r e c t a s y m p t o t i c f o r m
s i n c e t h e y c o n t a i n a l l open c h a n n e l s . T h i s i s e q u i v a l e n t to the s t a t e m e n t
538 BURKE
C A L I B R A T E D ELECTRON ENERGY SCALE eV
FIG. 1. Resonance structure observed in elastic e"-H scattering by McGowan et al. [Phys. Rev. Lett. _15
(1965) 918].
that the c o r r e s p o n d i n g o p t i c a l potential i s r e a l . We a l s o s e e t h a t t h e r e

a r e r e s o n a n c e s c o n v e r g i n g onto the n = 3 t h r e s h o l d in the s i x - s t a t e c a l c u l a -
tion. Again t h e s e a r i s e f r o m the d e g e n e r a t e dipole i n t e r a c t i o n . F i n a l l y
we note a f u r t h e r r e s o n a n c e j u s t above the n = 2 t h r e s h o l d . T h i s h a s the
c o n f i g u r a t i o n 2s2p 2 Р and i s a shape r e s o n a n c e f o r m e d by the a n g u l a r -
momentum barrier.
We show in F i g . 3 the I s - 2p excitation c r o s s - s e c t i o n c l o s e to t h r e s h o l d .
T h i s h a s s i m i l a r f e a t u r e s to t h e Is - 2s c r o s s - s e c t i o n .
Above the n = 3 t h r e s h o l d the 3 - s t a t e and the 6 - s t a t e c a l c u l a t i o n s
d i v e r g e . T h i s i s p r o b a b l y due to l o s s of flux into t h e n = 3 c h a n n e l s which
i s not t a k e n into account in the f o r m e r a p p r o x i m a t i o n . The I s - 2s e x c i t a -
tion up to 1000 eV i s shown in F i g . 4 . . The t h e o r i e s h e r e a r e c o m p a r e d with
the e x p e r i m e n t a l m e a s u r e m e n t s of Kauppila et al. (1970). The 3 - s t a t e
c a l c u l a t i o n i s in good a g r e e m e n t with e x p e r i m e n t below the n = 3 t h r e s h o l d
but i s in s e r i o u s e r r o r at i n t e r m e d i a t e e n e r g i e s . On t h e o t h e r hand, the
p s e u d o - s t a t e c a l c u l a t i o n by B u r k e and Webb (1970), which i n c l u d e s 3s and
3p type p s e u d o - s t a t e s a s well as the I s 2s and 2p a t o m i c e i g e n s t a t e s i s m o r e
satisfactory.
IAEA-SMR-12/17,19 5 3 9
n-Z n=3 n=4
10.5 II 11.5 12 125

Electron energy eV
FIG. 2. The Is - 2s e x c i t a t i o n cross-section close to threshold in e " - H scattering [Adv. At. Mol. Phys. 4
(1968) 2 1 2 ] .
/1-2 n-l n=4
To3 ÍLO ÍL5 ižlč ilÍT

Electron energy (ev)
FIG. 3. The Is - 2p e x c i t a t i o n cross-section close to threshold in e " - H scattering [ Atomic Processes in

Astrophysics (Eds Carson and Roberts) (1972) 2 1 ] .
540 BURKE
/ b state
|/Вогп\\
О N4
0
* \
0 ъ
aс » /S.
Pseudo-state
threshold
i t
Electron energy (eV)
FIG.4. The Is - 2s excitation cross-section from threshold to 1000 eV [J. Phys. B. (Atom. Molec. Phys.)
3 (1970) 1ЛЗГ).
FIG. 5. Bound states and autoionizing states of helium [Adv. At. Mol. Phys. 4(1968) 179].
IAEA-SMR-12/17,19 5 4 1
E l e c t r o n volts
Wavelength (angstroms)"
FIG. 6. Photon absorption cross-section in helium observed by Madden and Codling Astrophys. J. 141 (1965) 364.
з.3. E l e c t r o n s c a t t e r i n g by s i n g l y ionized h e l i u m
The m o s t i n t e r e s t i n g f e a t u r e of the e l a s t i c s c a t t e r i n g r e g i o n i s the

a p p e a r a n c e of r e s o n a n c e s below the n = 2 e x c i t a t i o n t h r e s h o l d . The s p e c -
t r u m of h e l i u m i s shown in F i g . 5 and we s e e t h a t t h e s e r e s o n a n c e s , or
a u t o i o n i z i n g s t a t e s , lie s o m e 60 eV above the ground s t a t e of h e l i u m .
T h e y w e r e f i r s t s e e n in i n e l a s t i c e l e c t r o n s c a t t e r i n g on h e l i u m in i t s ground
s t a t e but c a m e into p r o m i n e n c e following the work of Madden and Codling
(1963, 1965) who o b s e r v e d the Х Р r e s o n a n c e s e r i e s in photon a b s o r p t i o n
e x p e r i m e n t s in h e l i u m g a s u s i n g the N. B. S. s y n c h r o t r o n a s a s o u r c e of
и. v. p h o t o n s . F i g u r e 6 shows the a b s o r p t i o n s p e c t r u m which t h e y o b t a i n e d .
T h e s e r e s o n a n c e s have b e e n studied t h e o r e t i c a l l y e i t h e r by looking f o r the
e i g e n s o l u t i o n s of QHQ w h e r e Q p r o j e c t s onto the e x c i t e d s t a t e s of He + o r
by s o l v i n g the e" - He s c a t t e r i n g e q u a t i o n s . A r e v i e w of t h e s e a p p r o a c h e s
h a s b e e n given by B u r k e (1968). The p h y s i c a l m e c h a n i s m f o r t h e s e r e s o n a n -
c e s , a s in all i o n s , i s the l o n g - r a n g e Coulomb i n t e r a c t i o n which b i n d s the
s e c o n d e l e c t r o n t e m p o r a r i l y to the e x c i t e d He + ion. E n e r g y e x c h a n g e
b e t w e e n the two e l e c t r o n s a l l o w s one e l e c t r o n to d r o p into the I s s h e l l and
the o t h e r to e s c a p e , t y p i c a l l y in t i m e s of the o r d e r of 10" 14 s e c o n d s .
(b) _ls_r ?_s J-™? 2p _excit_ation
The p i c t u r e h e r e i s s i m i l a r to that f o r e" - H s c a t t e r i n g although i n d i c a -

t i o n s a r e that the e f f e c t of c l o s e d c h a n n e l s i s m o r e i m p o r t a n t in t h i s c a s e .
5 4 2 BURKE
Electron e n e r g y ( e v )
FIG.7. The I s - 2s e x c i t a t i o n cross-section close to threshold in e " - H e + scattering [J. Phys. B ( A t o m .

M o l e c . Phys.) 2 ( 1 9 6 9 ) 4 4 ] .
T h i s i s i l l u s t r a t e d f o r the I s - 2s c r o s s - s e c t i o n in F i g . 7 taken f r o m B u r k e
and T a y l o r (1969). R e c e n t m e a s u r e m e n t s by D o l d e r ( p r i v a t e c o m m u n i c a t i o n )
i n d i c a t e that t h i s c r o s s - s e c t i o n i s c o n s i d e r a b l y s m a l l e r than the I s - 2s - 2p -
p l u s - t w e n t y c o r r e l a t i o n - f u n c t i o n a p p r o x i m a t i o n c l o s e to t h r e s h o l d .
3.4. E l e c t r o n s c a t t e r i n g by a l k a l i m e t a l a t o m s
B e c a u s e of r e c e n t d e v e l o p m e n t s in the p r o d u c t i o n and d e t e c t i o n of
p o l a r i z e d b e a m s of a l k a l i a t o m s and e l e c t r o n s (e. g. K e s s l e r , 1969 and
F a r a g o , 1971) c o n s i d e r a b l e i n t e r e s t h a s b e e n f o c u s s e d on the t h e o r y of
spin-polarization measurements.
It i s a good a p p r o x i m a t i o n in c o n s i d e r i n g the l o w - e n e r g y s c a t t e r i n g
of e l e c t r o n s by a l k a l i a t o m s to a s s u m e that the c o r e e l e c t r o n s do not
e n t e r d y n a m i c a l l y into t h e c o l l i s i o n p r o c e s s , but i n s t e a d j u s t f o r m a s t a t i c
c h a r g e cloud which s c r e e n s t h e n u c l e u s . In t h i s c a s e the c o l l i s i o n r e d u c e s
to a t w o - e l e c t r o n p r o b l e m . In t h e c a s e of e l a s t i c s c a t t e r i n g E q . (1) b e c o m e s
C1 > .
+
XÛx^Je"*' L Vll> 4mi(1)xr(2)Mmim-2mim2(e2)l-
mi* m z
(53)
w h e r e o(£i) i s the wave f u n c t i o n f o r the v a l e n c e e l e c t r o n in the ground

s t a t e . The s c a t t e r i n g a m p l i t u d e M can be o b t a i n e d , in the c a s e w h e r e the
IAEA-SMR-12/17,19 543
s p i n - o r b i t i n t e r a c t i o n i s s m a l l by expanding the incident plane wave p a r t

of Eq. (53) in t e r m s of e i g e n s t a t e s of L and S. W r i t i n g M as a 4 X 4 m a t r i x
in the p r o d u c t space of the spin of the two e l e c t r o n , we find that
F(0) 0 0 0
0 j(F(0) + G(e» i(F(0)-G(O)) 0

(54)
M=
0 |(F(0)-G(e)) | ( F ( e ) + G(e)) 0
0 0 0 F(e)
w h e r e we have introduced the t r i p l e t s c a t t e r i n g amplitude
F(0) ^ (2 S + 1) (exp (2i6 J ) - 1) Р, (cos 0) (55)

l
and the singlet s c a t t e r i n g amplitude
(2i +
G(0) = X ( e x P ( 2 i ó í ) - x) p
{ (cos 0) (56)
I
If the exchange k e r n e l is z e r o then the p h a s e s h i f t s 6° = б J and M is diagonal

with no spin change. On the o t h e r hand, if t h i s k e r n e l i s n o n - z e r o we s h a l l
expect s p i n - p o l a r i z a t i o n e f f e c t s to o c c u r .
In the c a s e of p a r t i a l l y p o l a r i z e d b e a m s it i s convenient to i n t r o d u c e
the spin d e n s i t y m a t r i x for the two e l e c t r o n s y s t e m by
-3-1 А Л
= 1 + P a + +
P К I li ! i I Z q , °U°2i) <57>
i=1 i= 1 i. j = 1
w h e r e ст-ц and a 2i a r e the P a u l i spin m a t r i c e s f o r the atom and for the
incident e l e c t r o n , Вц is the initial spin p o l a r i z a t i o n of the atom b e a m ,
P 2i is the initial spin p o l a r i z a t i o n of the e l e c t r o n s , and Q^. i s a m a t r i x
which d e f i n e s the c o r r e l a t i o n of the s p i n s of the a t o m s and e l e c t r o n s .
The spin density m a t r i x d e s c r i b i n g the e l e c t r o n - a t o m s y s t e m a f t e r
the collision i s
p' = M p M + (58)
where M is the s c a t t e r i n g m a t r i x defined by (54). The p o l a r i z a t i o n s and

c o r r e l a t i o n s a f t e r the collision a r e then (Fano, 1957).
P'. = T r (р'ст н )/Тг p'
P ' . = T r ( p ' a 2 . ) / T r p' (59)
OL = T r (p'CTj.a^)/Tr p'
5 4 4 BURKE
w h e r e the d i f f e r e n t i a l s c a t t e r i n g c r o s s - s e c t i o n i s
о(9) = T r p' (60)
U s i n g t h e s e r e s u l t s it i s s t r a i g h t f o r w a r d to show (Burke and Schey, 1962)

that
a ( e ) P l k ( 6 ) = n ( e ) P l k + p(e.)P 2 k + ч(в) £ е...к<^
ii
<7(в)Р- к (0) = Р ( е ) Р 1 к + п ( в ) Р 2 к - q(6) J ] eij.kQ4 (61)

ij
+ +
atejQi.te) = т ( 0 ) б ц (i - X Q „ ) "WQij - q(e) Z ď i k - P8k>
i к
and
а(в) = k ( 0 ) + m(0) У Qn (62)
where
к(б} = i (3 I F I2 + |G|? )
m(0) = i ( | F | 2 - |G| 2 )
n(0) = j (2 I F | 2 + 2 R e (FG *)) (63)
p(0) = i ( 2 | f | 2 - 2 R e (FG *))
q(0) = I Im (FG *)
A n u m b e r of experiments* háve' b e e n c a r r i e d out r è c e n t l y involving

the s c a t t e r i n g of e l e c t r o n s f r o m p o t a s s i u m , a t o m s . Collins et al. (1971)
s c a t t e r e d u n p o l a r i z e d e l e c t r o n s off p o l a r i z e d a t o m s and m e a s u r e d the
p o l a r i z a t i o n of t h e a t o m s a f t e r the c o l l i s i o n . T h i s gives a m e a s u r e of
the d e p o l a r i z a t i o n r a t i o , which, a c c o r d i n g to E q s (62) and (63), i s
^ ^ Plk о(в) ~ 3 | F ( 6 ) | 2 + |G(0)|2 (64)
A c o m p a r i s o n with the t h e o r y of K a r u l e (1965, 1972) i s given in F i g . 8.

K a r u l e e v a l u a t e d the p h a s e s h i f t s f o r l i t h i u m , s o d i u m , p o t a s s i u m , a n d
c a e s i u m a t o m s u s i n g the ground s t a t e and the f i r s t e x c i t e d s t a t e s in a
IAEA-SMR-12/17,19 545
FIG. 8. The spin exchange scattering in e " - K measured by Collins et al. Phys. Rev. A3 (1971) 1976.
SCATTERING ANGLE (в)
FIG.9. The direct scattering in e"-K measured by Hils et al. [Phys. Rev. Lett. 29 (1972) 398].
c l o s e - c o u p l i n g e x p a n s i o n . Since, in the a l k a l i s , the f i r s t e x c i t e d s t a t e

a c c o u n t s f o r about 98% of the p o l a r i z a b i l i t y , in the s u m m a t i o n (44) we
e x p e c t the c a l c u l a t i o n s to be quite a c c u r a t e .
In a s e p a r a t e e x p e r i m e n t Hils et al. (1972) m e a s u r e d the p o l a r i z a t i o n
of i n i t i a l l y u n p o l a r i z e d e l e c t r o n s s c a t t e r e d f r o m s p i n - p o l a r i z e d p o t a s s i u m
a t o m s . T h i s g i v e s , a c c o r d i n g to E q s (62) and (63),
Р^к-Р(е) | F ( e ) + G(e) I2
P
lk сг(в) 3 | F ( 6 ) | 2 + |G(6)|2 1 J
5 4 6 BURKE
T h e i r m e a s u r e m e n t s a r e c o m p a r e d with K a r u l e ' s t h e o r y in F i g . 9.
E q u a t i o n s (64) and (65) can be put in a m o r e f a m i l i a r f o r m by i n t r o d u c i n g
the d i r e c t a m p l i t u d e f(0) and the exchange a m p l i t u d e g(0) by
f(6) = | ( F ( 0 ) + G(0)); g(0) = ! ( F ( Ô ) - G(fl)) (66)
It i s c l e a r t h a t the above two m e a s u r e m e n t s c o m b i n e d with a m e a s u r e m e n t

of the d i f f e r e n t i a l c r o s s - s e c t i o n i s s u f f i c i e n t to d e t e r m i n e t h e s e two a m p l i -
t u d e s t o g e t h e r with the p h a s e d i f f e r e n c e b e t w e e n t h e m .
(b) taelastic_scattering
T h e r e a r e f o u r i n d e p e n d e n t a m p l i t u d e s a s s o c i a t e d with the n s to np
e x c i t a t i o n p r o c e s s . U s i n g E q . (16) t h e s e a m p l i t u d e s can be w r i t t e n
^ W - K k V ? Z iL~ íz(2i>2 +
C1(!(L0;M-M)S^!insL У^(0ф)
' ' L£2=L±l (67)
Karule ond Peterkop
SCATTERING ANGLE (8)
FIG. 10. The ratio of spin-flip to total cross-section for inelastic e"-K scattering by Goldstein et al.
[Phys. Rev. A5 (1972) 660].
I A E A - S M R - 1 2 / 2 6 , 27 547
c o r r e s p o n d i n g to e x c i t a t i o n of the np s t a t e with m a g n e t i c q u a n t u m n u m b e r M
and t o t a l spin S. We note that f®a = ( f | j ) * which m e a n s that only two of the
t h r e e a m p l i t u d e s with M = + 1 , 0 , - 1 a r e in f a c t independent f o r e a c h value
of S.
In r e c e n t e x p e r i m e n t s by G o l d s t e i n et al. (1972) an u n p o l a r i z e d e l e c t r o n
b e a m w a s s c a t t e r e d off a p o l a r i z e d p o t a s s i u m b e a m and t h o s e a t o m s which
had b e e n e x c i t e d to the 4p s t a t e w e r e s p i n - a n a l y z e d a f t e r t h e i r s u b s e q u e n t
d e c a y . The f r a c t i o n of a t o m s whose s p i n s have changed can be e x p r e s s e d
in t e r m s of the a m p l i t u d e s (67) and the r e s u l t i s then c o m p a r e d with K a r u l e
and P e t e r k o p ' s (1965) t w o - s t a t e c l o s e - c o u p l i n g t h e o r y in F i g . 10. The
a g r e e m e n t b e t w e e n t h e o r y and e x p e r i m e n t i s now not quite a s good a s in
t h e e l a s t i c - s c a t t e r i n g c a s e , but i s s t i l l i m p r e s s i v e b e a r i n g in m i n d the
c o m p l e x i t y of the e x p e r i m e n t and the t h e o r y .
3.5. E l e c t r o n s c a t t e r i n g by np q a t o m s and i o n s
In m a n y i o n o s p h e r i c and a s t r o p h y s i c a l a p p l i c a t i o n s it i s i m p o r t a n t to
know the c r o s s - s e c t i o n f o r t r a n s i t i o n s b e t w e e n the g r o u n d - s t a t e t e r m s in
a t o m s and ions with c o n f i g u r a t i o n s
I s 2 2s 2 2p 4 and I s 2 2s 2 2p 6 3s 2 ЗрЧ (68)
with q = 2, 3 and 4. The t e r m s of i n t e r e s t a r e
3p 1
q= 2 S
4
s 2
D 2p
q= 3
q= 4 ap 2
S
which give r i s e to the s o - c a l l e d f o r b i d d e n l i n e s in the v i s i b l e s p e c t r u m .

E x a m p l e s a r e the line at 5577 Â due to the 1 S - хО e l e c t r i c q u a d r u p o l e
t r a n s i t i o n and the doublet at 6300, 6364 Â due to the XD - 3 P m a g n e t i c
dipole t r a n s i t i o n , both in a t o m i c oxygen, which give r i s e to the c h a r a c -
t e r i s t i c r e d and g r e e n l i n e s o b s e r v e d in t h e u p p e r a t m o s p h e r e .
A c o n s i d e r a b l e a m o u n t of work h a s b e e n c a r r i e d out including j u s t
the t h r e e g r o u n d - s t a t e t e r m s in a c l o s e - c o u p l i n g e x p a n s i o n and n e g l e c t i n g
a l l t e r m s a r i s i n g f r o m h i g h e r c o n f i g u r a t i o n s (Smith et al. , 1967 and
S a r a p h et al. , 1969). T a b l e I i n d i c a t e s t h e n u m b e r of coupled c h a n n e l s
that o c c u r s in t h i s c a s e f o r e" - O s c a t t e r i n g . We s e e that only S = 1 / 2
c o n t r i b u t e s to i n e l a s t i c s c a t t e r i n g w h e r e a s we n e e d to include S = 3 / 2
a s well when c o n s i d e r i n g e l a s t i c s c a t t e r i n g on the ground s t a t e . F o r e a c h
L it i s n e c e s s a r y to c o n s i d e r a s e t of f o u r and a s e t of five coupled e q u a t i o n s
in the c a s e of i n e l a s t i c s c a t t e r i n g .
H o w e v e r , the e f f e c t of e x c i t e d c o n f i g u r a t i o n s can be i m p o r t a n t a s the
e x c i t a t i o n c r o s s - s e c t i o n s f o r e" - N s c a t t e r i n g shown in F i g . 11 i n d i c a t e s .
The s o l i d c u r v e s a r e obtained including j u s t t e r m s of the I s 2 2s 2 2p 3 c o n -
f i g u r a t i o n in t h e c l o s e - c o u p l i n g e x p a n s i o n while the d a s h e d c u r v e s , c a l c u l a t e d
5 4 8 BURKE
T A B L E I. THE C O U P L E D CHANNELS FOR e~- О FOR EACH

L S 7Г COMBINATION
L+l
rr = ( - 1 )
и
S = i
i s 2 2s 2 2 p 4 3
P .». = L «j = L + 1, L - 1
1
Is 2 2s 2 2 p 4 *D ^ = 1 + 2, L, L - 2 í j = L + 1, L - 1
Is 2 2s 2 2 p 4 *S -
ьS - -2i T = ("1)L tt = ( - 1 ) L + 1
Is 2 2s 2 2 p 4 3
P f - L Sj = L + 1, L - 1
О 5.0 IO.O 15.0 20.0 25.0
Incident Electron Energy
F I G . 11. I n e l a s t i c s c a t t e r i n g of e l e c t r o n s on a t o m i c n i t r o g e n c a l c u l a t e d by O r m o n d e e t a l . ( 1 9 7 3 ) .
by O r m o n d e et al. (1973), include coupling with the f i r s t e x c i t e d c o n f i g u r a -

tion I s 2 2s 2 2p 2 ( 3 P ) 3s ( 4 , 2 P ) . This g i v e s a m a x i m u m of 9 coupled i n t e g r o -
d i f f e r e n t i a l e q u a t i o n s in the m o s t c o m p l i c a t e d c a s e . We s e e that the e f f e c t
of coupling with the h i g h e r c o n f i g u r a t i o n r e d u c e s the e x c i t a t i o n c r o s s -
s e c t i o n s p a r t i c u l a r l y c l o s e to t h r e s h o l d although f u r t h e r w o r k m u s t be done to
confirm this result.
I A E A - S M R - 1 2 / 2 6 , 27 549
FIG. 12. E f f e c t of r e s o n a n c e s on e ~ - 0 2 + i n e l a s t i c c o l l i s i o n s c a l c u l a t e d by Eissner e t a l . [ J . Phys. B.

( A t o m . M o l e c . Phys.) 2 (1969) 3 4 1 ] .
A n o t h e r e x c i t e d c o n f i g u r a t i o n of i m p o r t a n c e , p a r t i c u l a r l y f o r i o n s ,
w h e r e t h e r e i s d e g e n e r a c y f o r l a r g e Z , i s I s 2 2s 2p q + 1 . In the c a s e of
a t o m i c oxygen t h i s g i v e s r i s e to only two t e r m s J P and 3 P , h o w e v e r f o r
0 2 + , which i s of p a r t i c u l a r i m p o r t a n c e in c e r t a i n g a s e o u s nebulae, we have
six t e r m s 5 S , 3 S , 3 D, 1 D , 3 P , a n d x P . It i s c l e a r t h a t the n u m b e r of a d d i t i o n a l
coupled c h a n n e l s which would be i n t r o d u c e d by t h i s c o n f i g u r a t i o n i s
formidable.
E i s s n e r et a l . (1969) have i n v e s t i g a t e d the e f f e c t of the Is 2 2s 2p 3 3 P
and I s 2 2s 2p 3 3 D c o n f i g u r a t i o n s on t r a n s i t i o n s in 0 2 + involving the g r o u n d -
s t a t e c o n f i g u r a t i o n . T h e i r r e s u l t s f o r the c o l l i s i o n s t r e n g t h s a r e shown
in F i g . 12. T h e y found that a I s 2 2s 2 p 3 3 P 3s 2 P r e s o n a n c e l i e s j u s t above
the 1 S t h r e s h o l d and a I s 2 2s 2p 3 3D 3s 2 D r e s o n a n c e l i e s j u s t above the 1 D
t h r e s h o l d . We s e e t h a t the c o l l i s i o n s t r e n g t h s including the r e s o n a n c e s
a r e s i g n i f i c a n t l y a l t e r e d f r o m the r e s u l t s , i n d i c a t e d by d a s h e d l i n e s , obtained
e a r l i e r by S a r a p h et al. (1969) who c o n s i d e r e d j u s t the ground c o n f i g u r a t i o n .
The above e x a m p l e s show t h a t t h e r e i s s t i l l a c o n s i d e r a b l e a m o u n t of
w o r k to be done to c l a r i f y the r o l e of h i g h e r c o n f i g u r a t i o n s on t r a n s i t i o n s
involving the g r o u n d - s t a t e c o n f i g u r a t i o n .
5 5 0 BURKE
4. ATOMIC PHOTOIONIZATION P R O C E S S E S
4.1. Introduction
With the advent of l a s e r s and the r e a d y a v a i l a b i l i t y of s y n c h r o t r o n

r a d i a t i o n a s s o u r c e s of p h o t o n s t h e r e h a s b e e n a c o n s i d e r a b l e i n c r e a s e in
the l a s t few y e a r s in the study of a t o m i c photoionization p r o c e s s e s . F r o m
the t h e o r e t i c a l point of view the m a i n i n t e r e s t h a s b e e n in the i n f o r m a t i o n
that such a study y i e l d s about the d y n a m i c s of the a t o m , p a r t i c u l a r l y in the
c o n t i n u u m . On the o t h e r hand, f r o m a m o r e p r a c t i c a l s t a n d p o i n t , such
s t u d i e s a r e i m p o r t a n t in an a t t e m p t to u n d e r s t a n d the t r a n s p o r t of r a d i a t i o n
t h r o u g h g a s e s and the r o l e that such p r o c e s s e s p l a y in the p r o p e r t i e s of
l a b o r a t o r y and a s t r o p h y s i c a l p l a s m a s . In addition it h a s been r e a l i z e d in
the l a s t few y e a r s , t h a t , with a s u i t a b l e choice of p a r a m e t e r s , t h e o m i t t e d
p h o t o e l e c t r o n s m a y be highly p o l a r i z e d and c o n s e q u e n t l y p r o v i d e a c o n -
venient s o u r c e of s p i n - p o l a r i z e d e l e c t r o n s . In t h i s s e c t i o n we will a t t e m p t
to look at s o m e of t h e s e a s p e c t s by a n a l y z i n g r e c e n t e x p e r i m e n t s u s i n g
d e v e l o p m e n t s in the t h e o r y m a d e in the l a s t few y e a r s .
4.2. T h e o r y of p h o t o e l e c t r o n a n g u l a r d i s t r i b u t i o n s
The b a s i c p h o t o i o n i z a t i o n p r o c e s s t h a t we a r e studying i s
h v + A, - A | + e' (70)
In g e n e r a l we c o n s i d e r a b e a m of p h o t o n s which a r e l i n e a r l y p o l a r i z e d in
the z - d i r e c t i o n and the p h o t o e l e c t r o n s e m i t t e d at s o m e a z i m u t h a l angle 0
a s i l l u s t r a t e d in F i g . 13. The a t o m and r e s i d u a l ion a r e at 0 and the o u t -
going p h o t o e l e c t r o n i s e m i t t e d in direction_k.
We now d e r i v e an e x p r e s s i o n f o r the c r o s s - s e c t i o n u s i n g a p r o c e d u r e
s i m i l a r to t h a t u s e d by H e n r y and L i p s k y (1967), C o o p e r and Z a r e (1969),
and J a c o b s (1972). The photoionization c r o s s - s e c t i o n can be w r i t t e n in a
n u m b e r of d i f f e r e n t f o r m s . The dipole length a p p r o x i m a t i o n i s
2
a L ( 0 ) = 4тi 2 a a 2 w | <ФТ|е-М 1 |-Ф 1 > (71)
w h e r e M j i s the e l e c t r i c - d i p o l e length o p e r a t o r
i N+1
(72)
F I G . 13. T h e basic p h o t o i o n i z a t i o n p r o c e s s .
I
Photon
IAEA-SMR-12/17,19 551
The dipole v e l o c i t y a p p r o x i m a t i o n i s
2
(73)
w
w h e r e M 2 i s the e l e c t r i c - d i p o l e v e l o c i t y o p e r a t o r
N+l
(74)
i= l
T h e s e two f o r m s give i d e n t i c a l r e s u l t s when e x a c t wave f u n c t i o n s a r e u s e d ,

but one of t h e m m a y be p r e f e r a b l e to the o t h e r when a p p r o x i m a t e wave
f u n c t i o n s a r e adopted. T h u s the length f o r m t e n d s to e m p h a s i z e the long-
r a n g e p a r t of the wave f u n c t i o n while the v e l o c i t y f o r m g i v e s m o r e weight
to s h o r t e r d i s t a n c e s . In both (71) and (73), £ d e f i n e s the i n c i d e n t photon
p o l a r i z a t i o n which in the c a s e c o n s i d e r e d in F i g . 13 i s
% = (0, 1, 0 ) (75)
F u r t h e r , a i s the f i n e - s t r u c t u r e c o n s t a n t , w i s the photon e n e r g y in

R y d b e r g s , a 0 i s the B o h r r a d i u s of the h y d r o g e n a t o m , Ф; i s the n o r m a l i z e d
wave f u n c t i o n of the a t o m and Ф j i s the f i n a l s c a t t e r i n g s t a t e wave f u n c t i o n
d e s c r i b i n g the m o t i o n of the outgoing p h o t o - e l e c t r o n in the field of the
r e s i d u a l ion. The n o r m a l i z a t i o n of Ф." i s defined by
< Ç ( k 2
) |Ф". ( k ' 2
)>= 6 (к2 - k'2)6... (76)
and the b o u n d a r y condition c o r r e s p o n d s to an outgoing wave in c h a n n e l j

and ingoing w a v e s in all c h a n n e l s . In a n a l o g y with E q s . (1) and (13) t h i s
h a s the f o r m
Ф? = ф . . + ф.. (7
*) inc ingoing *
w h e r e Ф. i n c c o r r e s p o n d s to a p l a n e wave, now m o d i f i e d by the l o n g - r a n g e

Coulomb i n t e r a c t i o n , in d i r e c t i o n k.
If we a s s u m e t h a t L and S a r e s e p a r a t e l y c o n s e r v e d , then we can
expand Ф". in t e r m s of the c h a n n e l f u n c t i o n s i n t r o d u c e d by E q . (6). We
f i n d , in analogy with (14), t h a t
LS í j m f .
a L
k k V k
m*
X Y £ Ц (ft) $ k ( X l . . . X N l N ^ N - ^ r - ^ u j g (r N + 1 ) (78)
5 5 2 BURKE
w h e r e s i i s the u s u a l a n t i s y m m e t r i z a t i o n o p e r a t o r and the r e q u i r e d

n o r m a l i z a t i o n in E q . (76) gives
U
W ( r )
r - ТЩ ( e
"i0kSki -ei6V (79)
The Coulomb d i s t o r t e d wave m u s t be u s e d in t h i s c a s e and so
e = k r l n 2 +
k K - H * - \ V - % (80)
where
a i k = a r g r ( j > k + 1 + ±rjk) (81)
and
If the c l o s e - c o u p l i n g a p p r o x i m a t i o n i s u s e d to c a l c u l a t e the r a d i a l
f u n c t i o n s Ujj, it i s convenient to u s e K - m a t r i x b o u n d a r y conditions s i n c e
the r e s u l t a n t f u n c t i o n s a r e t h e n r e a l . We t h e r e f o r e w r i t e (79) in the
completely equivalent f o r m
1
u" (r) (sin 0 + c o s 0 K) (1 + i K ) (83)
w h e r e we have u s e d m a t r i x notation f o r k, 9 and K.

In o r d e r to s i m p l i f y the r e s u l t a n t e x p r e s s i o n s f o r the d i f f e r e n t i a l
c r o s s - s e c t i o n we now i n t r o d u c e the ket v e c t o r s
KJLJSJÍJ L S M L M S > = J* £ ФК(Х1. . .^«WW1™ ukj(rN+1) (84)

L s f
°k k k k
and
leiLiSiM4Ms1> =
Vxi----xN+1) (85>
We then u s e the W i g n e r - E c k a r t t h e o r e m to w r i t e the m a t r i x e l e m e n t t h a t

o c c u r s in E q s (71) and (73) a s
<AJ.L.SJLSMLMS|M|J LAIBISJML. MS. > = ( 2 L + 1 ) ' 4

C L 1 (LM L ; ML.FJ)
X <ajLjSjLS||M||QiLiSi>6SSiôMsMs (86)
I A E A - S M R - 1 2 / 2 6 , 27 553
w h e r e we have u s e d t h e notation of F a n o and R a c a h (1959) f o r the r e d u c e d

matrix elements.
The d i f f e r e n t i a l c r o s s - s e c t i o n f o r p h o t o i o n i z a t i o n of an u n p o l a r i z e d
a t o m by a p o l a r i z e d photon b e a m , w h e r e the s p i n s of the p h o t o e l e c t r o n
and the r e s i d u a l ion a r e not o b s e r v e d , f o l l o w s f r o m (71) o r (73) by
s u m m i n g o v e r f i n a l m a g n e t i c q u a n t u m n u m b e r s and a v e r a g i n g o v e r
i n i t i a l m a g n e t i c q u a n t u m n u m b e r s . In the dipole length a p p r o x i m a t i o n
t h i s gives
2
I K ^ M J - » (37)
MTL j MCb j
M t . M C Ш;
J
h
and we obtain an e q u i v a l e n t r e s u l t in the dipole v e l o c i t y a p p r o x i m a t i o n .

The e v a l u a t i o n of t h i s e x p r e s s i o n in t e r m s of the r e d u c e d m a t r i x e l e m e n t s
d e f i n e d in E q . (86) can be c a r r i e d out u s i n g the s t a n d a r d t e c h n i q u e s of
R a c a h ' s a l g e b r a . We find that
сг(в) = (1 + ß p (cos в)) (88)

4 JT "
w h e r e the t o t a l p h o t o i o n i z a t i o n c r o s s - s e c t i o n
2
Í k w ^ l K I k b Ä ) ! (39)
L f
j
and the a s y m m e t r y p a r a m e t e r
4тт 2 а a ' w L + L Д " 1 .£,• - С!

a = 1 1 eXp }
tct0 (2Li + l) A
LL 1
e-c-
уi 1
X [(2L + 1) (2L' + 1) (2jPj + 1 ) (2jP/ + 1 ) ] 2 W ( L i j L'jPj'; L } 2) W ( 1 L 1 L ' ; L ; 2)
X Cj j . (2 0; 0 0) С ц ( 2 0; 0 0) < a j L j S j L S 11 M j | Lj Sj>
X < a . L . S ^ I L ' S H m J I or. L j S j ) * (90)
That the f i n a l r e s u l t f o r the a n g u l a r d i s t r i b u t i o n m u s t indeed have the

f o r m defined by E q . (88) f o l l o w s f r o m a g e n e r a l i n v a r i a n c e a r g u m e n t f i r s t
given by Yang (1948). The b a s i c a s s u m p t i o n s m a d e in h i s d e r i v a t i o n a r e
f i r s t l y that only one d i r e c t i o n in s p a c e i s s p e c i f i e d b e f o r e t h e a b s o r p t i o n
t a k e s p l a c e , in t h i s c a s e t h i s d i r e c t i o n i s the photon p o l a r i z a t i o n d i r e c t i o n ,
s e c o n d l y that only f i n a l s t a t e s of a given p a r i t y a r e p r e s e n t , and t h u s o d d - i
c o n t r i b u t i o n s which a r i s e f r o m i n t e r f e r e n c e e f f e c t s b e t w e e n s t a t e s of
opposite p a r i t y will be a b s e n t , and f i n a l l y t h a t s i n c e the a b s o r p t i o n t a k e s
p l a c e via an e l e c t r i c - d i p o l e t r a n s i t i o n the v a l u e s of Л a r e r e s t r i c t e d to
0 and 2.
554 BURKE
If the p h o t o n s a r e u n p o l a r i z e d we can obtain t h e r e s u l t a n t a n g u l a r

d i s t r i b u t i o n by a s s u m i n g that the incident b e a m i s c o m p o s e d of an i n c o h e r e n t
m i x t u r e of two b e a m s l i n e a r l y p o l a r i z e d at r i g h t a n g l e s . U s i n g E q . (88) f o r
both b e a m s we find that the d i f f e r e n t i a l c r o s s - s e c t i o n i s
o(0) = ( 1 - i ß P 2 ( c o s в)) (91)
w h e r e 0 i s now the a z i m u t h a l angle defined r e l a t i v e to the incident photon

b e a m d i r e c t i o n and a and ß a r e given, a s b e f o r e , by E q s (89) and (90),
respectively.
The r e q u i r e m e n t that both c r o s s - s e c t i o n s (88) and (91) a r e p o s i t i v e
o r z e r o at all a n g l e s i m p l i e s t h a t
- 1 S ß S 2 (92)
We s e e f r o m the above t h a t an a n a l y s i s of p h o t o e l e c t r o n a n g u l a r - d i s t r i b u t i o n
m e a s u r e m e n t s will yield two e n e r g y - d e p e n d e n t q u a n t i t i e s to c o m p a r e with
theory.
4.3. R e c e n t r e s u l t s f o r the t o t a l c r o s s - s e c t i o n and the

asymmetry parameter
The s p e c t r a l d i s t r i b u t i o n of the t o t a l photoionization c r o s s - s e c t i o n h a s

b e e n f u l l y r e v i e w e d by F a n o and Cooper (1968). We t h e r e f o r e l i m i t our
d i s c u s s i o n h e r e to s o m e r e c e n t work which i l l u s t r a t e s the t h e o r e t i c a l
d e v e l o p m e n t in the p r e v i o u s s e c t i o n .
о 2 4 6 8 10 „
Ю 12 16
WAVELENGTH X ( 1 0 0 0 Ä)
FIG. 14. T h e p h o t o i o n i z a t i o n c r o s s - s e c t i o n of H - [ B r a n s c o m b , L . M . , i n Physics of t h e O n e - and T w o -

electron Atoms (Int. Symp. M u n i c h , Sept. 1968) A m s t e r d a m , North-Holland Publishing C o . (1969) 6 9 4 ] .
I A E A - S M R - 1 2 / 2 6 , 27 5 5 5
(a) Plwtoion^îon_of_H_and_He
The n e g a t i v e h y d r o g e n ion i s the d o m i n a n t s o u r c e of o p a c i t y in the

s o l a r a t m o s p h e r e and i s a l s o i m p o r t a n t in the a t m o s p h e r e of m a n y o t h e r
s t a r s . E a r l y work w a s c a r r i e d out by C h a n d r a s e k h a r (1945) and the m o s t
d e t a i l e d study h a s b e e n m a d e by Doughty et al. (1966) who u s e d a 7 0 - t e r m
H y l l e r a a s wave f u n c t i o n f o r H" and a I s 2s 2p 3s 3p 3d c l o s e - c o u p l i n g wave
f u n c t i o n f o r the f i n a l s t a t e . The c a l c u l a t e d p h o t o i o n i z a t i o n c r o s s - s e c t i o n
i s shown in F i g . 14. We s e e t h a t t h e r e i s a b r o a d m a x i m u m s t r e t c h i n g f r o m
t h e u . v . to the i n f r a - r e d and, in addition, a s h a r p peak o c c u r s at 1129.54 A
c o r r e s p o n d i n g to t h e X P r e s o n a n c e j u s t above the n = 2 t h r e s h o l d . T h i s
r e s o n a n c e i s a l s o s e e n in e"- H s c a t t e r i n g in F i g s 2 and 3.
If the photon e n e r g y i s s u f f i c i e n t l y l a r g e then the r e s i d u a l a t o m o r ion
m a y be l e f t in an e x c i t e d s t a t e . Close to the n = 2 t h r e s h o l d m o r e than 10%
of all He + ions a r e l e f t in e i t h e r the 2s o r the 2p s t a t e s . We show in F i g . 15
t h e n = 2 p h o t o i o n i z a t i o n c r o s s - s e c t i o n s f o r H" and f o r the He ground s t a t e
t a k e n f r o m the w o r k of H y m a n et al. (1972). The c a l c u l a t i o n s w e r e c a r r i e d
out u s i n g 5 6 - t e r m H y l l e r a a s grounds-state wave f u n c t i o n s and I s 2s 2p c l o s e -
coupling f i n a l - s t a t e wave f u n c t i o n s . Close to t h r e s h o l d p h o t o i o n i z a t i o n
l e a v i n g the r e s i d u a l a t o m o r ion in a 2p s t a t e i s m o r e p r o b a b l e than p h o t o -
ionization to the 2s s t a t e , a r e s u l t which i s in d i s a g r e e m e n t with c a l c u l a t i o n s
which do not include the e f f e c t s of c l o s e coupling b e t w e e n the d e g e n e r a t e
f i n a l s t a t e s . At high e n e r g i e s it i s p o s s i b l e to show t h a t the p h o t o i o n i z a t i o n
c r o s s - s e c t i o n s a r e d o m i n a t e d by t r a n s i t i o n s to s - s t a t e s which b e h a v e ~ к 7
while t h o s e to p - s t a t e s b e h a v e ~ k" 9 .
FIG. 15. T h e n = 2 p h o t o i o n i z a t i o n c r o s s - s e c t i o n for H " and H e c a l c u l a t e d by H y m a n e t a l . [ J . Phys. В

( A t o m . M o l e c . Phys.) 5 ( 1 9 7 2 ) 2282 ] .
5 5 6 BURKE
Ejected Electron Energy, Rydbergs
FIG. 16. ß2 f o r p h o t o i o n i z a t i o n f r o m t h e H e 1 1 S 2 s S a n d 2 ' s s t a t e s c a l c u l a t e d by J a c o b s and Burke ( 1 9 7 2 ) .
Owing to t h e d e g e n e r a c y of the 2s and 2p s t a t e s it i s not p o s s i b l e to

d i s t i n g u i s h e x p e r i m e n t a l l y b e t w e e n t h e s e two f i n a l s t a t e s by o b s e r v i n g the
e n e r g y of t h e p h o t o e l e c t r o n . H o w e v e r , t h e y can be d i s t i n g u i s h e d if the
a n g u l a r d i s t r i b u t i o n i s m e a s u r e d , since ß f o r the 2s s t a t e can be shown
to be a l w a y s 2 f r o m a n g u l a r - m o m e n t u m c o n s e r v a t i o n , while ß f o r the 2p
s t a t e can have any value c o n s i s t e n t with E q . (92). C a l c u l a t i o n s by J a c o b s
and B u r k e (1972) of ß 2 p a r e shown in F i g . 16 f o r p h o t o i o n i z a t i o n f r o m the
1 1 S , 2 3 S and 2 J S s t a t e s of h e l i u m . The r e s u l t s obtained f o r the 1 J S s t a t e
a r e c o n s i s t e n t with a n g u l a r d i s t r i b u t i o n m e a s u r e m e n t s by K r a u s e and
W u i l l e u m i e r (1972). We s e e t h a t in the h i g h - e n e r g y l i m i t ß2p i s t e n d i n g
to 2 in all t h r e e c a s e s so t h a t the a n g u l a r d i s t r i b u t i o n f a i l s , in t h i s l i m i t ,
to d i s t i n g u i s h b e t w e e n the 2s and 2p s t a t e s .
(b) Photoionization_ofJSIe and_Ar
We now d i s c u s s s o m e r e c e n t r e s u l t s which i n d i c a t e the i m p o r t a n c e of

c o n f i g u r a t i o n i n t e r a c t i o n in the p h o t o i o n i z a t i o n of i n n e r - s h e l l e l e c t r o n s .
The m a i n p r o c e s s e s of i n t e r e s t h e r e a r e f i r s t l y p h o t o i o n i z a t i o n of the o u t e r
p - s h e l l e l e c t r o n , e. g.
hv + N e ( l s 2 2 s 2 2 p 6 1 S ) - N e + ( l s 2 2 s 2 2 p 5 2 P ) + e _ ( k s , kd) (93)
I A E A - S M R - 1 2 / 2 6 , 27 557
w h e r e o u r notation i m p l i e s that the p h o t o e l e c t r o n i s in an s o r a d - w a v e

continuum o r b i t a l , and s e c o n d l y p h o t o i o n i z a t i o n of the i n n e r s - s h e l l
e l e c t r o n , e . g.
hv + Ne ( I s 2 2 s z 2 p 6 ^ - N e + ( l s 2 2s 2p 6 2 S)+ e" (kp) (94)
M e a s u r e m e n t s of the a n g u l a r d i s t r i b u t i o n of the o u t e r p - s h e l l p h o t o -
e l e c t r o n in the 0 - 2 0 eV r a n g e above t h r e s h o l d have b e e n c a r r i e d out u s i n g
s y n c h r o t r o n r a d i a t i o n f o r neon by Lynch et al. (1972) and f o r a r g o n by
M i t c h e l l and Codling (1972), The e x p e r i m e n t a l r e s u l t s f o r a r g o n a r e shown
a s open c i r c l e s in F i g . 17 w h e r e t h e y a r e c o m p a r e d with the t h e o r e t i c a l
r e s u l t s of Kennedy and M a n s o n (1972). The t h e o r e t i c a l c a l c u l a t i o n s w e r e
c a r r i e d out in the H a r t r e e - F o c k a p p r o x i m a t i o n n e g l e c t i n g c h a n n e l coupling.
We s e e t h a t the a g r e e m e n t i s v e r y s a t i s f a c t o r y .
On the o t h e r hand s o m e r e c e n t m e a s u r e m e n t s have b e e n m a d e of the
A r 3 s - s u b s h e l l p h o t o i o n i z a t i o n c r o s s - s e c t i o n by L y n c h et al. (1973). T h e s e
a r e c o m p a r e d with H a r t r e e - F o c k c a l c u l a t i o n s of Kennedy and Manson (1972)
and c a l c u l a t i o n s by A m u s i a et al. (1972) in F i g . 18. T h e r e a r e s t r o n g i n d i c a -
t i o n s h e r e t h a t the H a r t r e e - F o c k a p p r o x i m a t i o n i s not a d e q u a t e . In the work
of A m u s i a et al. coupling b e t w e e n t h e d i r e c t n s -» kp e x c i t a t i o n (see Eq. 94)
and the np -* kd e x c i t a t i o n (see E q . 93) i s allowed f o r u s i n g the r a n d o m - p h a s e
a p p r o x i m a t i o n with e x c h a n g e . It i s c l e a r t h a t t h i s c o n s i d e r a b l y i m p r o v e s
the a g r e e m e n t with e x p e r i m e n t .
In concluding t h i s b r i e f r e v i e w of r e c e n t work we note that i n c r e a s i n g
e m p h a s i s i s b e i n g given to the r o l e t h a t c o n f i g u r a t i o n i n t e r a c t i o n in the
continuum p l a y s in p h o t o i o n i z a t i o n p r o c e s s e s .
PHOTOELECTRON ENERGY (EV)
FIG. 17. ß for p h o t o i o n i z a t i o n of t h e З р - e l e c t r o n i n Ar m e a s u r e d by M i t c h e l l and C o d l i n g (O). Other e x p e r i -

m e n t a l v a l u e s a r e Berkowitz a n d E h r h a r d t ( • ), V r o o m e t al. ( • ) , S a m s o n ( A ) , M o r g e n s t e r n e t a l . (•),
Carlson and Jonas ( A ) . T h e s o l i d l i n e s show t h e t h e o r e t i c a l r e s u l t s of K e n n e d y a n d M a n s o n . (From Phys. L e t t .
38A (1972) 3 1 . )
5 5 8 BURKE
0.8
ARGON
3- 0.6
5
с
о
25
Photoelectron E n e r g y (e V )
F I G . 18. T h e 3s s u b - s h e l l p h o t o i o n i z a t i o n c r o s s - s e c t i o n i n Ar m e a s u r e d b y L y n c h e t a l . ( 1 9 7 3 ) .
4.4. R e s o n a n c e s in p h o t o i o n i z a t i o n p r o c e s s e s
We have a l r e a d y s e e n that r e s o n a n c e s p l a y an i m p o r t a n t r o l e in e l e c t r o n -
a t o m c o l l i s i o n p r o c e s s e s . In t h i s s e c t i o n we will s t u d y in g r e a t e r d e t a i l t h e
e f f e c t of r e s o n a n c e s on p h o t o i o n i z a t i o n c r o s s - s e c t i o n s . A f u n d a m e n t a l p a p e r
in t h i s a r e a h a s b e e n w r i t t e n by F a n o (1961) and the e f f e c t of r e s o n a n c e s on
the p h o t o i o n i z a t i o n of the r a r e g a s e s h a s b e e n c o n s i d e r e d by F a n o and
C o o p e r (1965).
We will t a k e a s our m o d e l the i n t e r a c t i o n of one d i s c r e t e s t a t e ф with
one c o n t i n u u m фЕ. T h i s d e s c r i b e s the s i t u a t i o n d i s c u s s e d in s e c t i o n 3.3
w h e r e a n u m b e r of well s e p a r a t e d d i s c r e t e : Р r e s o n a n c e s t a t e s in h e l i u m
i n t e r a c t with the I s kp continuum and h a s a l s o b e e n c o n s i d e r e d in a
s i m i l a r context by M o i s e i w i t s c h (1973). We a s s u m e t h a t
<Ф, Ф£> = О (95)
and t h a t the e x p e c t a t i o n of the H a m i l t o n i a n in the s p a c e of t h e s e s t a t e s i s

given by
<Ф, H ф> = E
<(//Е, H </>>= vE (86)
<(//„, H ФЕ,У = E ' 6 ( E " - E')

I A E A - S M R - 1 2 / 2 6 , 27 559
The l a s t e q u a t i o n i m p l i e s that the H a m i l t o n i a n h a s b e e n p r e - d i a g o n a l i z e d in

the s p a c e of the continuum s t a t e s . T h i s r e s t r i c t i o n i s not e s s e n t i a l and the
m o d i f i c a t i o n of the t h e o r y to e l i m i n a t e it h a s b e e n m a d e by F a n o and
P r a t s (1963).
We now d i a g o n a l i z e the e n e r g y m a t r i x d e f i n e d by (96). We w r i t e the
corresponding eigenfunction as
Ф Е = аф + J d E ' b E . ^ E , (97)
T h i s m u s t s a t i s f y the S c h r ö d i n g e r equation
(H - E ) Ф Е = 0 (98)
which g i v e s , on p r e - m u l t i p l y i n g by ф and фЕ and i n t e g r a t i n g o v e r the s p a c e

of all e l e c t r o n s
E,a+ /dE'VEïbE. = Ea
(99)
VE.a + E'bE. = E b E ,
w h e r e we have u s e d E q . (96). T h e r e i s an i n f i n i t e set of l i n e a r s i m u l t a n e o u s

e q u a t i o n s f o r the c o e f f i c i e n t s a and b E . Solving the s e c o n d f o r m a l l y gives
bE. = ( ^ T g r +Z(E)o(E-E'))V E , a (100)
w h e r e P i s the p r i n c i p a l v a l u e and Z(E) d e p e n d s on t h e contour of i n t e g r a t i o n

r o u n d the s i n g u l a r i t y at E = E '.
If the s t a t e s фЕ a r e r e p r e s e n t e d by a wave f u n c t i o n with the a s y m p t o t i c
behaviour
Фе ~ s i n (kr + 6« (E)) (101)
w h e r e 6 0 (E) i s a slowly v a r y i n g p o t e n t i a l p h a s e s h i f t , then our t o t a l wave

f u n c t i o n h a s t h e a s y m p t o t i c f o r m , f r o m E q s (97) and (100),
% ~ J dE b E , фЕ,
— [ - 7Г c o s (kr + 6 0 ) + Z (E) sin (kr + 5 0 )] VE a (102)
~ VE a •Jtt2 + Z 2 s i n (kr + 60 + 6t )
560 BURKE
w h e r e we have d e f i n e d a r e s o n a n t p h a s e s h i f t by
6r (E) = - t a n ' 1 (103)
Substituting (100) into the f i r s t of E q s (99) then gives
Z ( E ) = E - E - A ( E )
I V
E i
w h e r e the l e v e l s h i f t Д (E) i s given by
Г I I2
Д(Е) = P J iJ^'J, dE' (105)
It f o l l o w s t h a t the r e s o n a n t p h a s e shift i n c r e a s e s r a p i d l y t h r o u g h тг r a d i a n s
in the n e i g h b o u r h o o d of the r e s o n a n t e n e r g y E = E 0 + Д .
In o r d e r to c a l c u l a t e the photoionization t r a n s i t i o n m a t r i x e l e m e n t f r o m
s o m e i n i t i a l s t a t e i to the f i n a l r e s o n a n t s t a t e ФЕ we need e x p l i c i t e x p r e s s i o n s
f o r a and b E . . The c o e f f i c i e n t a can be obtained by s u b s t i t u t i n g E q . (100) into
Eq. (97) and u s i n g
<Ф Е , Ф Е , > = б ( Е - Е ' ) (106)
which g i v e s
s n ž
- i г
a =
* V E
The r e q u i r e d m a t r i x e l e m e n t i s
<ФЕ|т |i> = — < Ф | M j i > sin6r - O e I M J O cos 6 r (108)

7Г V E
where
Ф=ф+ p/dE' (109)
which i s the s t a t e ф m o d i f i e d by an a d m i x t u r e of continuum s t a t e s . The

c o r r e s p o n d i n g p h o t o i o n i z a t i o n c r o s s - s e c t i o n i s then given by
I A E A - S M R - 1 2 / 2 6 , 27 561
2
g K ^ E I M J O I _ g + e
CT 2 2 ( U 0 )
0 " K ^ l M j i ) ! " ! ^
where
E E
e = - cot 6 r = —TF 1 - 1
(111)
2
and the l i n e - p r o f i l e index o r r e s o n a n t shape p a r a m e t e r
< ф IM, | i >

q = , i , 1 r - ; j г — ^ (112)
тг<ф | H I ^ X ^ J M J Í )
The line p r o f i l e index d e p e n d s on the r e l a t i v e s i g n s and m a g n i -

t u d e s of the t h r e e m a t r i x e l e m e n t s o c c u r r i n g in E q . (112) and i s t h u s a
s e n s i t i v e t e s t of t h e o r y . In p r i n c i p l e q can have any v a l u e r a n g i n g f r o m
- oo to + oo. If q 2 < 1 then the c o r r e s p o n d i n g c r o s s - s e c t i o n s h o w s a n e t
d e c r e a s e in t h e n e i g h b o u r h o o d of the r e s o n a n c e , with the c o n t i n u u m o s c i l l a t o r
s t r e n g t h b e i n g r e p e l l e d . On t h e o t h e r hand, if q 2 > 1 then the t o t a l c r o s s -
s e c t i o n shows a n e t i n c r e a s e in t h e n e i g h b o u r h o o d of the r e s o n a n c e . We
should n o t e , h o w e v e r , t h a t the t o t a l o s c i l l a t o r s t r e n g t h i s l e f t i n v a r i a n t
s i n c e (97) i s a u n i t a r y t r a n s f o r m a t i o n .
P r o b a b l y the c l o s e - c o u p l i n g a p p r o x i m a t i o n h a s b e e n c o n s i s t e n t l y t h e
m o s t s u c c e s s f u l t h e o r y in c a l c u l a t i n g the r e s o n a n c e p a r a m e t e r s , although
s o m e n u m e r i c a l w o r k b a s e d d i r e c t l y on the m a t r i x d i a g o n a l i z a t i o n t e c h n i q u e
d i s c u s s e d above h a s b e e n c a r r i e d out b y A l t i c k and M o o r e (1966) and by
A l t i c k (1968). In the c l o s e - c o u p l i n g a p p r o x i m a t i o n the continuum s t a t e s
t/£ a r e r e p r e s e n t e d by the open c h a n n e l s and the d i s c r e t e s t a t e s a r e r e p r e -
s e n t e d by t h e c l o s e d c h a n n e l s . T h e s e s t a t e s a r e e s s e n t i a l l y e i g e n s t a t e s of
QHQ w h e r e Q i s now c h o s e n to p r o j e c t onto the c l o s e d c h a n n e l s in the c l o s e -
coupling e x p a n s i o n . In t h e c a s e of He good a g r e e m e n t h a s b e e n o b t a i n e d with
m e a s u r e m e n t s m a d e by Madden and Codling (1963, 1965), d i s c u s s e d in
s e c t i o n 3.3, by B u r k e and M c V i c a r (1965) who u s e d the I s - 2s - 2p a p p r o x i -
m a t i o n to r e p r e s e n t ФЕ and a 2 0 - t e r m H y l l e r a a s wave f u n c t i o n f o r the ground
state.
In the g e n e r a l c a s e w h e r e t h e r e i s m o r e than one continuum and w h e r e
the r e s o n a n c e s m a y o v e r l a p , the above d i s c u s s i o n l e a d i n g to E q s (110),
(111) and (112) n e e d s e x t e n d i n g . An a n a l y s i s in t h i s c a s e h a s a l s o b e e n
given by F a n o (1961) and m o r e r e c e n t l y by S h o r e (1967, 1968).
4.5. P r o d u c t i o n of s p i n - p o l a r i z e d e l e c t r o n s
P h o t o i o n i z a t i o n in the h e a v y a l k a l i m e t a l s i s s t r o n g l y i n f l u e n c e d by
the s p i n - o r b i t i n t e r a c t i o n . Many y e a r s ago F e r m i (1930) pointed out t h a t
it i s t h e c a u s e of the a n o m a l o u s l y high doublet line s t r e n g t h r a t i o s f o r t h e
d i s c r e t e p r i n c i p a l s e r i e s t r a n s i t i o n s . L a t e r , Seaton (1951) e x t e n d e d t h i s
d i s c u s s i o n into the c o n t i n u u m and showed t h a t t h e s p i n - o r b i t i n t e r a c t i o n
e x p l a i n s the n o n - z e r o m i n i m a o b s e r v e d in t h e p h o t o i o n i z a t i o n c r o s s - s e c t i o n s ,
while r e c e n t l y F a n o (1969a, b) p r e d i c t e d that the e f f e c t could be u s e d to
562 BURKE
p r o d u c e b e a m s of highly p o l a r i z e d e l e c t r o n s by p h o t o i o n i z a t i o n , u s i n g
c i r c u l a r l y p o l a r i z e d light. T h i s h a s b e c o m e known a s t h e F a n o e f f e c t .
The s p i n - o r b i t i n t e r a c t i o n can p l a y an e n h a n c e d r o l e in two c i r c u m -
s t a n c e s . F i r s t l y , if the a m p l i t u d e s a r e v a r y i n g with e n e r g y r a p i d l y a s
n e a r a r e s o n a n c e and s e c o n d l y if the a m p l i t u d e s a r e s m a l l . It i s t h i s
l a t t e r c i r c u m s t a n c e t h a t o c c u r s in the a l k a l i s . Close to the continuum
t h r e s h o l d in Cs both a m p l i t u d e s l e a d i n g to continuum and continuum
P 3 / 2 s t a t e s p a s s t h r o u g h z e r o , h o w e v e r s i n c e t h e s e z e r o s do not o c c u r
at the s a m e e n e r g y t h e r e i s a l i m i t e d r a n g e of e n e r g i e s w h e r e the two
a m p l i t u d e s have s m a l l v a l u e s of opposite sign. In t h i s e n e r g y r a n g e
strongly polarized photoelectrons are produced.
The m a t r i x e l e m e n t s involved in the p h o t o i o n i z a t i o n p r o c e s s c o r r e s -
ponding to r i g h t - c i r c u l a r l y p o l a r i z e d light a r e p r o p o r t i o n a l to
М =
,-т-,ш 3 <кРЗт;К|б8т3> (113)
w h e r e m s i s the spin o r i e n t a t i o n of the bound e l e c t r o n in the i n i t i a l s t a t e

and w h e r e m.1 = m s + 1. In o r d e r to c a l c u l a t e the spin p o l a r i z a t i o n , t h i s
a m p l i t u d e m u s t be w r i t t e n in t e r m s of the m a g n e t i c quantum n u m b e r s of
the outgoing e l e c t r o n u s i n g the r e s u l t
|jm!>= ^ C l { (j т . ; m^m^) (114)
A f t e r s u m m i n g o v e r both j v a l u e s and i n t e g r a t i n g o v e r a l l a n g l e s of t h e
outgoing e l e c t r o n we find t h a t the r e q u i r e d spin m a t r i x i s
В.я (R 3 - Rj)
M m
(115)
sms
+ 2 R
i (R3 1>
w h e r e R j and R 3 a r e the r a d i a l i n t e g r a l s
Rj = / P ( k p i ; r ) rP(6s|;r)dr
0
(116)
R3 = J P ( k p | ; r) r P ( 6 s i ; r) dr
0
If the s p i n - o r b i t i n t e r a c t i o n i s z e r o then R j = R 3 and M m s . m s i s d i a g o n a l .

It f o l l o w s t h a t t h e r e i s no spin p o l a r i z a t i o n in t h i s c a s e . The spin p o l a r i z a -
tion when R j f R 3 can be e a s i l y c a l c u l a t e d f r o m (115) to give
I A E A - S M R - 1 2 / 2 6 , 27 563
where the p a r a m e t e r
= 2 9 + ] 1 1 8
* r R ( >
3 ~ 1
h a s b e e n i n t r o d u c e d by F a n o (1969a) to c h a r a c t e r i z e the p o l a r i z a t i o n e f f e c t .
F i n a l l y , e q u i v a l e n t q u a n t i t i e s which can be m e a s u r e d a r e the ion counting
r a t e a s y m m e t r y f o r i o n i z a t i o n of s p i n - p o l a r i z e d a t o m s by a l t e r n a t e l y l e f t
and r i g h t c i r c u l a r l y p o l a r i z e d light
Q - f H <119>
o r the d e g r e e of spin p o l a r i z a t i o n of e j e c t e d p h o t o e l e c t r o n s f o r ionization

of s p i n - p o l a r i z e d a t o m s with light p o l a r i z e d l i n e a r l y , p e r p e n d i c u l a r to and
p a r a l l e l to the spin q u a n t i z a t i o n a x i s
x 2
R±=
" л(6) (120)
and
R л ( 6 )
n - <121>
In t h e s e e q u a t i o n s the f u n c t i o n Д (6 ) i s
w h e r e б = б j/2 - б 3 / 2 with 6j the p h a s e s h i f t of the kpj continuum s t a t e .
[ R e p . P r o g t . P h y s . 34 ( 1 9 7 1 ) 1 1 1 6 ] .
5 6 4 BURKE
T h i s s m a l l c o r r e c t i o n is r e q u i r e d (Fano, 1969b) by the p h a s e r e n o r m a l i z a -

tion of the p h o t o e l e c t r o n wave f u n c t i o n s , i . e . M j m . i m s = | м | e l 6 i .
The F a n o e f f e c t h a s been t e s t e d e x p e r i m e n t a l l y by K e s s l e r and L o r e n z
(1970) and by H e i n z m a n n et a l . (1970) who m e a s u r e d P , and by L u b e l l and
R a i t h (1969) and B a u m et a l . (1970) who m e a s u r e d Q. TJie m e a s u r e m e n t s
of H e i n z m a n n et al. a r e c o m p a r e d with F a n o ' s p r e d i c t i o n in F i g . 19 and it
i s s e e n that t h e a g r e e m e n t i s e x c e l l e n t .
In c o n c l u s i o n we c o m m e n t that with the advent of the l a s e r b e a m s of
high i n t e n s i t y it m a y be e x p e c t e d that m u l t i p h o t o n ionization p r o c e s s e s
will be studied m o r e in the f u t u r e . Some p r e l i m i n a r y work in t h i s d i r e c t i o n
h a s a l r e a d y b e e n c a r r i e d out (e. g. L a m b r o p o u l o s , 1972, K l a r s f e l d and
M a q u e t , 1972, and F a i s a l , 1972) and it i s c l e a r t h a t t h i s a r e a will be m o s t
fruitful.
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IAEA - S M R - 1 2 / 2 6 , 2 7
COLLISIONS B E T W E E N E L E C T R O N S
AND M O L E C U L E S
F . H . READ
Manchester University,
Manchester, United Kingdom
Abstract
COLLISIONS BETWEEN ELECTRONS AND MOLECULES.

1. E x p e r i m e n t a l t e c h n i q u e s ( g u n s , e l e c t r o n l e n s e s , e n e r g y s e l e c t o r s and a n a l y s e r s , d e t e c t o r s , coincidence
methods); 2. D e t e r m i n a t i o n of s y m m e t r i e s of e l e c t r o n i c s t a t e s of n e g a t i v e m o l e c u l a r ions ( s h a p e and
F e s h b a c h r e s o n a n c e s , a n g u l a r d i s t r i b u t i o n t h e o r y , s y m m e t r i e s of N 2 and C 0 2 r e s o n a n c e s , s e l e c t i o n r u l e s for
electronic transitions); 3. D e t e r m i n a t i o n of p o t e n t i a l f u n c t i o n s ( d e p e n d e n c e of c r o s s - s e c t i o n s on F r a n c k -
C o n d o n o v e r l a p f a c t o r s , d e t e r m i n a t i o n f r o m t h e e x p e r i m e n t a l d a t a of potential functions of excited states of
H | ); 4. R o t a t i o n a l t r a n s i t i o n s in r e s o n a n c e r e a c t i o n s ( s e l e c t i o n r u l e s for r o t a t i o n a l t r a n s i t i o n s , r o t a t i o n a l
t r a n s i t i o n s for H i , s y m m e t r i e s of s t a t e s of H 2 ); 5. D e t e r m i n a t i o n of g e n e r a l i z e d o s c i l l a t o r s t r e n g t h s f o r
t r a n s i t i o n s in n e u t r a l m o l e c u l e s ( g e n e r a l i z e d o s c i l l a t o r s t r e n g t h , r e g i o n of v a l i d i t y of Born a p p r o x i m a t i o n ,
d e p e n d e n c e of g e n e r a l i z e d o s c i l l a t o r s t r e n g t h o n e l e c t r o n i c s y m m e t r y , d e t e r m i n a t i o n f r o m c r o s s - s e c t i o n
m e a s u r e m e n t s , p e c u l i a r b e h a v i o u r of £ + — XT t r a n s i t i o n s ) ; 6. D e t e r m i n a t i o n of l i f e t i m e s of e x c i t e d s t a t e s
of n e u t r a l m o l e c u l e s by e l e c t r o n - s c a t t e r i n g m e t h o d s ( t h e e l e c t r o n - p h o t o n c o i n c i d e n c e t e c h n i q u e , v a r i a t i o n of
l i f e t i m e w i t h v i b r a t i o n a l q u a n t u m n u m b e r , d e p e n d e n c e of e l e c t r o n i c o s c i l l a t o r s t r e n g t h on i n t e r n u c l e a r
d i s t a n c e , n o r m a l i z a t i o n of c r o s s - s e c t i o n d a t a ) ; 7 . P r e i o n i z i n g s t a t e s of n e u t r a l m o l e c u l e s ( e j e c t e d e l e c t r o n s
f r o m a t o m s , e j e c t e d electrons f r o m m o l e c u l e s , c o m p a r i s o n with p h o t o i o n i z a t i o n results).
INTRODUCTION
T h e r e a r e v e r y m a n y t o p i c s w h i c h could be d i s c u s s e d in the f i e l d of
e l e c t r o n - m o l e c u l e c o l l i s i o n s , but h e r e we c o n c e n t r a t e on t h o s e e l e c t r o n
s c a t t e r i n g e x p e r i m e n t s which give n e w i n f o r m a t i o n about the p r o p e r t i e s
óf m o l e c u l e s . In o t h e r w o r d s , we s h a l l t r e a t e l e c t r o n s c a t t e r i n g a s a
spectroscopic technique for investigating molecules.
F o r e x a m p l e , we now know q u i t e a lot about n e g a t i v e m o l e c u l a r i o n s
s u c h a s H2, Ng and COg, and m u c h of t h i s k n o w l e d g e h a s b e e n o b t a i n e d
f r o m electron s c a t t e r i n g e x p e r i m e n t s . The electronically excited s t a t e s
of s u c h i o n s a r e f o r m e d a s s h o r t - l i v e d r e s o n a n c e s in e l e c t r o n - m o l e c u l e
c o l l i s i o n s , and it i s p o s s i b l e to a n a l y s e t h e d a t a f r o m t h e s e r e s o n a n c e
e x p e r i m e n t s to o b t a i n t h e s y m m e t r y c l a s s i f i c a t i o n s of the e x c i t e d s t a t e s .
T h i s a n a l y s i s r e q u i r e s a k n o w l e d g e of s o m e a n g u l a r c o r r e l a t i o n t h e o r y ,
w h i c h we s h a l l c o n s i d e r l a t e r ; we s h a l l s e e t h a t t h i s t h e o r y g i v e s r i s e to
v a r i o u s s e l e c t i o n r u l e s f o r , f o r e x a m p l e , e l e c t r o n i c and r o t a t i o n a l t r a n s i -
t i o n s , and t h a t the s e l e c t i o n r u l e s e n a b l e t h e s y m m e t r i e s of s t a t e s to b e
d e t e r m i n e d . T h e e x p e r i m e n t a l d a t a h a v e a l s o b e e n u s e d to d e t e r m i n e t h e
e n e r g i e s , l i f e t i m e s and p o t e n t i a l c u r v e s of e x c i t e d s t a t e s , and we s h a l l
d e s c r i b e t h e way in w h i c h t h i s h a s b e e n d o n e . T h e s e e l e c t r o n s c a t t e r i n g
e x p e r i m e n t s p r o v i d e a u n i q u e way of s t u d y i n g s u c h m o l e c u l e s — in e f f e c t
a n e w t y p e of s p e c t r o s c o p i c t e c h n i q u e .
We s h a l l a l s o d e a l with t h e s t u d y of n e u t r a l m o l e c u l e s — p a r t i c u l a r l y
with d i a t o m i c m o l e c u l e s . H e r e a g a i n e l e c t r o n s c a t t e r i n g e x p e r i m e n t s c a n
be u s e d to i n v e s t i g a t e t h e p r o p e r t i e s of e x c i t e d s t a t e s . F o r e x a m p l e ,
"•"Present a d d r e s s : J o i n t I n s t i t u t e for L a b o r a t o r y A s t r o p h y s i c s , U n i v e r s i t y o f C o l o r a d o , Boulder, C o l . 8 0 3 0 2 , USA.
567
5 6 8 ' READ
s y m m e t r i e s can be deduced f r o m a n g u l a r - d i s t r i b u t i o n s t u d i e s , o s c i l l a t o r
s t r e n g t h s can be found f r o m c r o s s - s e c t i o n m e a s u r e m e n t s , and l i f e t i m e s
can be obtained f r o m e l e c t r o n - p h o t o n c o i n c i d e n c e m e t h o d s . The t h e o r y
u n d e r l y i n g t h e s e v a r i o u s m e t h o d s , and a l s o a p p l i c a t i o n s to s p e c i f i c m o l e -
c u l e s will be c o n s i d e r e d .
If e x c i t e d s t a t e s of n e u t r a l m o l e c u l e s have enough e n e r g y then they m i g h t
d e c a y by e j e c t i n g e l e c t r o n s . T h e s e p r e i o n i z i n g (or autoionizing) s t a t e s can
a l s o be s t u d i e d t h r o u g h e l e c t r o n s c a t t e r i n g e x p e r i m e n t s . P o r e x a m p l e , s o m e
p r e i o n i z i n g s t a t e s of N2 have r e c e n t l y b e e n o b s e r v e d .
T h e s e l e c t u r e n o t e s have been w r i t t e n f o r v e r b a l p r e s e n t a t i o n , and give
only an i n t r o d u c t i o n to t h e s u b j e c t . No a t t e m p t h a s b e e n m a d e t o give c o m -
p r e h e n s i v e r e f e r e n c e s to the work in the f i e l d .
1. E X P E R I M E N T A L TECHNIQUES
F i g u r e 1 s h o w s a d i a g r a m of a t y p i c a l e l e c t r o n s c a t t e r i n g a p p a r a t u s .
We s h a l l d e s c r i b e in t u r n the gun, e l e c t r o n l e n s e s , s e l e c t o r , a n a l y s e r ,
d e t e c t o r , and m o l e c u l a r b e a m . Then we s h a l l d e a l with the v a r i o u s m o d e s
of o p e r a t i o n of c o m p l e t e s p e c t r o m e t e r s .
FIG. 1. D i a g r a m of e l e c t r o n s c a t t e r i n g a p p a r a t u s ( f r o m C o m e r a n d R e a d , 1971),
I A E A - S M R - 1 2 / 2 6 , 27 5 6 9
FIG.2. Electron energy distribution. E l e c t r o n s in t h e d a r k - s h a d e d r e g i o n a r e r e m o v e d by t h e e n e r g y

s e l e c t o r , e l e c t r o n s in t h e l i g h t - s h a d e d r e g i o n a r e r e m o v e d by d e f i n i n g a p e r t u r e s .
E l e c t r o n gun
The s o u r c e of e l e c t r o n s i s e i t h e r a hot t u n g s t e n f i l a m e n t o r an o x i d e -
coated c a t h o d e . The e n e r g y d i s t r i b u t i o n of the e m i t t e d e l e c t r o n s i s shown
in F i g . 2. Not a l l t h e s e e l e c t r o n s r e a c h the t a r g e t . T h o s e which have a
t r a n s v e r s e m o m e n t u m which i s too l a r g e a r e r e m o v e d by defining a p e r t u r e s
and s o m e of the r e m a i n i n g e l e c t r o n s a r e r e m o v e d by the e n e r g y s e l e c t o r .
Only a n a r r o w band of e n e r g i e s i s allowed to r e a c h the t a r g e t . The e n e r g y
s p r e a d of t h i s band i s t y p i c a l l y b e t w e e n 15 m e V and 70 m e V (1 m e V = 10" 3 e
and the c u r r e n t in the b e a m , at the t a r g e t , i s t y p i c a l l y ~ 10"10 a m p at
15 m e V r e s o l u t i o n , and 10" 7 a m p at 70 m e V r e s o l u t i o n .
Electron-optical lenses
A f t e r l e a v i n g the gun the e l e c t r o n s p a s s t h r o u g h l e n s e s . In f a c t t h e r e

a r e l e n s e s in m a n y d i f f e r e n t p l a c e s in the d i a g r a m of F i g . 1. T h e s e l e n s e s
a r e n e a r l y a l w a y s e l e c t r o s t a t i c . F i g u r e 3 s h o w s a double c y l i n d e r l e n s .
Two o t h e r g e o m e t r i e s a r e shown in F i g . 4. In f a c t m a n y o t h e r g e o m e t r i e s
have a l s o b e e n u s e d .
FIG. 3. F o c u s s i n g of d o u b l e - c y l i n d e r l e n s . E l e c t r i c - f i e l d l i n e s ( i n d i c a t i n g d i r e c t i o n of a c c e l e r a t i o n ) in t h e
coaxial cylinders; F = b e a m focus.
5 7 0 ' READ
( a )
v. V,
p a
FIG. 4 . G e o m e t r y of e l e c t r o n - o p t i c a l l e n s e s , (a) Double-aperture lens; (b) triple-cylinder lens with

a s y m m e t r i c v o l t a g e s ( V j i V2 / V 3 ) ; P = object distance, Q = image distance.
The 3 - e l e m e n t l e n s e s a r e p a r t i c u l a r l y i m p o r t a n t , and r e c e n t l y
a lot of work h a s b e e n done in developing t h e m . The m i d d l e e l e m e n t a d d s
an e x t r a d e g r e e of f r e e d o m which gives t h e m m u c h m o r e f l e x i b i l i t y than i s
the c a s e f o r d o u b l e - e l e m e n t l e n s e s . F o r e x a m p l e in m a n y a p p l i c a t i o n s one
m a y want to keep V j , P and Q c o n s t a n t whilst V 3 i s changed, and t h i s can
be a c h i e v e d by a l t e r i n g V2 a p p r o p r i a t e l y . T h i s i s the s o - c a l l e d " z o o m l e n s "
m o d e which i s so u s e f u l when e n e r g i e s at the t a r g e t n e e d to be changed
without a l t e r i n g the f i n a l p o s i t i o n of f o c u s .
Energy selector
The s e l e c t o r shown in F i g . 1 i s an e l e c t r o s t a t i c h e m i s p h e r i c a l s e l e c t o r .
The way in which it o p e r a t e s i s shown in F i g . 5. A p e r t u r e s a r e p l a c e d at
the e n t r a n c e and exit of the s e l e c t o r (these a r e c o n j u g a t e p o i n t s ) to d e f i n e
x m , and o t h e r a p e r t u r e s d e f i n e a m , and so t h e m a x i m u m e n e r g y s p r e a d
which can p a s s t h r o u g h the s e l e c t o r i s l i m i t e d to t h a t shown. O t h e r t y p e s
of s e l e c t o r can a l s o be u s e d : s o m e a r e shown in F i g . 6.
Energy analysers
T h e s e c o m e a f t e r the s c a t t e r i n g p r o c e s s , and a r e the s a m e i n s t r u m e n t s

a s the e n e r g y s e l e c t o r s .
IAEA-SMR-12/26, 27 571
CENTRAL RAY ( CIRCULAR PATH )

ENERGY E
4>V,
FIG. 5. Electrostatic hemispherical energy selector. If ray В h a s e n e r g y E 0 + ДЕ ( ДЕ « E0 ) t h e n

(xi + xz)/2ro + a2 = ДЕ/Ео.
FIG, 6. O t h e r t y p e s of s e l e c t o r , (a) Cylindrical analyser; (b) p a r a l l e l - p l a t e mirror analyser; (c) cylindrical-

m i r r o r a n a l y s e r ( d a s h e d l i n e d e n o t e s axis of s y m m e t r y ) .
572 ' READ
ELECTRON
BEAM
(Q)
CHANNEL ELECTRON MULTIPLIER [OR CHANNELTRONI
SECONDARY ELECTRONS
FIG. 7. T w o t y p e s of d e t e c t o r s , (a) Simple Faraday cup to detect total current, (b) Channel electron
multiplier ( c h a n n e l t r o n ) w i t h OV a t i n l e t ( I ) and 2 - 3 k V at o u t l e t ( O ) ; At О t h e r e a r e ~ 1 0 6 t o 10 8 s e c o n d a r y
e l e c t r o n s per i n c i d e n t e l e c t r o n . C h a n n e l w a l l s of b l a c k glass ( ~ 2 m m d i a m . , ~ 4 c m long).
GAS IN
INCIDENT
SCATTERED
ELECTRON BEAM
BEAM
Y
OAS OUT
GAS BEAMS'
cos 0
DISTRIBUTION
OF ATOMS DISTRIBUTION
P E A K E D IN
FORWARD
/DIRECTION
SIMPLE TUBE OR HYPODERMIC

NEEDLE ARRAY OF F I N E CAPILLARIES
F I G . 8. T w o t y p e s of gas t a r g e t s , c e l l and b e a m s .
IAEA- S M R - 1 2 / 2 6 , 2 7 573
U
к 200
/ v
1.0 2.0 3.0 4.0
ENERGY LOSS (eV)
FIG. 9. Electron-impact spectrometer spectrum. E n e r g y - l o s s s p e c t r u m for e l e c t r o n s s c a t t e r e d f r o m H 2 .

I n c i d e n t e n e r g y 1 2 . 4 7 e V , s c a t t e r i n g a n g l e 70° ( f r o m C o m e r a n d R e a d , 1971).
Detectors
Two t y p e s a r e shown in F i g . 7.
Gas t a r g e t s
Two t y p e s a r e shown in F i g . 8.
Modes of o p e r a t i o n of c o m p l e t e e l e c t r o n i m p a c t s p e c t r o m e t e r s
The s i m p l e s t m o d e i s the e n e r g y l o s s m o d e . H e r e the i n c i d e n t e n e r g y

E ; of the e l e c t r o n s i s kept c o n s t a n t , and the e n e r g y Ef of the s c a t t e r e d
e l e c t r o n s i s s c a n n e d by the e n e r g y a n a l y s e r . F i g . 9 s h o w s an e x a m p l e f r o m
H 2 , f o r v i b r a t i o n a l e x c i t a t i o n , and F i g . 10 s h o w s r o t a t i o n a l e x c i t a t i o n . T h i s l a s t
example r e p r e s e n t s the best energy resolution that has ever been achieved
s o f a r in t h i s t y p e of e x p e r i m e n t . T h e s e s p e c t r a will b e c o n s i d e r e d l a t e r .
574 ' READ
-J О 1Л из
î î < A î Î î î Î
<R> (SJ <
C
M <*>
H
2
25°
RES0L.= 17 meV
«100
. I
!.. I
\.n i
r 1\
\
0.1 "' 0 0.1 0.2

ENERGY LOSS, eV
F1G. 10. E n e r g y - l o s s s p e c t r u m ( r o t a t i o n a l e x c i t a t i o n ) in H 2 > for i n c i d e n t e n e r g y 1 1 . 0 7 e V

(from Joyez et a l . , 1973).
A n o t h e r m o d e i s the r e s o n a n c e m o d e . H e r e the e n e r g y l o s s E ; - Ef i s
kept c o n s t a n t (for e x a m p l e , it m a y be z e r o , which would m e a n e l a s t i c
s c a t t e r i n g ) and the i n c i d e n t e n e r g y E t i s s c a n n e d by t h e s e l e c t o r . F i g u r e s 11
and 12 show e x a m p l e s of r e s o n a n c e s p e c t r a .
Yet a n o t h e r m o d e i s t h e e m i s s i o n m o d e . H e r e E^ - E^ i s kept c o n s t a n t
(as in t h e r e s o n a n c e m o d e ) , but i t s value d o e s not c o r r e s p o n d to any e x c i t a -
tion e n e r g y of the t a r g e t a t o m o r m o l e c u l e . T h e r e f o r e i n e l a s t i c s c a t t e r i n g
p r o c e s s e s a r e not d e t e c t e d . E l e c t r o n s e j e c t e d f r o m p r e i o n i z i n g s t a t e s a r e
d e t e c t e d h o w e v e r , and the e m i s s i o n m o d e i s u s e f u l f o r t h e s t u d y of such
s t a t e s . F i g u r e 13 s h o w s an e x a m p l e in N 2 .
Coincidence methods
F i g u r e 14 s h o w s the b a s i s of an e l e c t r o n - p h o t o n c o i n c i d e n c e m e t h o d
f o r m e a s u r i n g l i f e t i m e s , and F i g . 15 s h o w s t h e e x p e r i m e n t a l o b s e r v a t i o n s .
Note the f l a t b a c k g r o u n d of u n c o r r e l a t e d e v e n t s .
I A E A - S M R - 1 2 / 2 6 , 27 5 7 5
v=l
-= 3
v J К
x I
I/=4
x 2
5
x 2
-л
ПО И-5 120 12-5 130 13-5 140
C o l l i s i o n energy ( e V )
F I G . 11. E x a m p l e of r e s o n a n c e s p e c t r a in H 2 ( f r o m C o m e r a n d R e a d , 1 9 7 1 ) .
576 ' READ
1 1 1 1 1 1 |- Г Г 1 ' 1 1 ! ••
1 1 1 ^ SERIES С
v=0 1 2
I I 1 1 •
0 1 2 3
SERIES A'
•V
Д v =0
90°
ûv = 4
25» .
i i i i i i 1 1 î "1 1 )
11.0 11.5 * 12.0
INCIDENT ENERGY (eV)
FIG. 12. Example of resonance spectra in H2 (from Joyez et al., 1973).
2. DETERMINATION OF SYMMETRIES OF ELECTRONIC STATES

OF NEGATIVE MOLECULAR IONS
B e f o r e s t a r t i n g on t h e m o r e f o r m a l a c c o u n t of a n g u l a r d i s t r i b u t i o n s ,
and t h e way in which t h e y can give s y m m e t r i e s , we s h a l l give a s i m p l e
p i c t o r i a l d e s c r i p t i o n of t h e p h y s i c a l m e c h a n i s m .
C o n s i d e r t h e r e s o n a n c e at about 2.3 e V in e - N2 s c a t t e r i n g
e + N 2 (V ; = 0) N 2 ( v r ) - N 2 ( v f = 0) + e (elastic)
(2.1)
o r -> N 2 ( v j f 0) + e (inelastic)
IAEA-SMR-12/26, 27 577
-i—I 1 1 1 1 1 1 1 1 1 1 1—i г-
VfV '• »
0'9 10 II 1-2
v0
NPI к ' .
у 0
NPi
v
у'-г
0
v.
-1 ' NPI
1"0
1
NP2 _1 I 1 1...
2 I у-О
-1 1
Î ' NP2 Л 2 f
v
J
. ?. —;—' Ai
>1 J! NP3 ^=2 j
с ji !l
о
и ч' '•"•Л- !
Ct,
ш i VV: '"Ví\ i Л - А ,4л Л ft
v . ••" •' v- •
: < ' v^
> 4 /
« V * 2 I ^ =0
• 4 iÔ ~ ' " '
I \>-0 u , 1 л ,
_j I H /77 я 3 K-O
" v
*i , Л V «í * А • '
10 1-5 20 2-5 30
Ejected electron energy ( e V )
F I G . 13. E j e c t e d e l e c t r o n s p e c t r a for N z ( f r o m Hicks e t a l . , 1973).

5 7 8 ' READ
XV 2
1
v=0
CO
FIG. 1 4 . E l e c t r o n - p h o t o n c o i n c i d e n c e m e t h o d for l i f e t i m e m e a s u r e m e n t s ,
e + A ~ A* + e its d e t e c t i o n used to s t a r t t i m i n g
A''~= A + hi*-» its d e t e c t i o n used t o stop t i m i n g thus m e a s u r i n g t i m e A t b e t w e e n t h e t w o d e t e c t i o n e v e n t s .
12000
P\
10000
Í
со
Z
8000
J
20 40 60 80
CHANNEL NUMBER
FIG. 1 5 . E x p e r i m e n t a l results o b t a i n e d with c o i n c i d e n c e m e t h o d ( f r o m Imhof a n d R e a d , 1 9 7 1 b ) .

I A E A - S M R - 1 2 / 2 6 , 27 579
Electron Energy (eV)
FIG, 16. E n e r g y d e p e n d e n c e of c r o s s - s e c t i o n t o v a r i o u s v i b r a t i o n a l s t a t e s . Cross-sections plotted on s a m e

r e l a t i v e s c a l e , t h e a b s o l u t e s c a l e is a r b i t r a r y ( a f t e r S c h u l z ( 1 9 6 2 ) ) .
580 READ
75
125
v=3
50 E= 2.1 eV
100 V«1
E = 1.9eV
25
75
0 30 60 90 120
£ 50
v= 3
t 25
m E=3.1eV
30 60 90 120°
<
oc
о
100
0 30 60 90 120°
v=1
E=2.8 eV
75
v=5
50 E = 2.2eV
0 30 60 90 120° 0 30 60 90 120°
SCATTERING ANGLE
FIG. 17. A n g u l a r d i s t r i b u t i o n of i n e l a s t i c s c a t t e r i n g ( v = 1, 3, 5) of e l e c t r o n s f r o m N 2 for s e v e r a l f i x e d

i m p a c t e n e r g i e s E. Errors c o n t a i n c o m m o n n o r m a l i z a t i o n and r e p r o d u c i b i l i t y of a l l c u r v e s
( f r o m Ehrhardt a n d W i l l m a n n , 1967).
F i g u r e 16 s h o w s the f i r s t m e a s u r e m e n t s b y Schulz (1962) and F i g . 17

s h o w s the a n g u l a r d i s t r i b u t i o n s m e a s u r e d by E h r h a r d t and W i l l m a n n (1967).
We s h a l l s e e what can be deduced f r o m t h e s e a n g u l a r d i s t r i b u t i o n s .
The m o l e c u l e N 2 h a s the e l e c t r o n i c c o n f i g u r a t i o n
K K ( C T g 2 s ) 2 ( a u 2 s ) 2 (тг и 2р) 4 (a g 2p) 2
and the next (unfilled) m o l e c u l a r o r b i t a l i s тг_2p which h a s the s y m m e t r y

I A E A - S M R - 1 2 / 2 6 , 27 581
It s e e m s t h a t when the i n c i d e n t e l e c t r o n h a s an e n e r g y of about 2.3 e V

it c a n o c c u p y t h i s u n f i l l e d o r b i t a l to f o r m t h e m o l e c u l e N 2 . T h i s m o l e c u l e
then exists for a short time 10~ 14 s) b e f o r e b r e a k i n g up into an e l e c t r o n
and N 2 ( p e r h a p s in an e x c i t e d v i b r a t i o n a l s t a t e ) .
T h i s t y p e of r e s o n a n c e , in w h i c h t h e e l e c t r o n s of t h e t a r g e t m o l e c u l e
s t a y in t h e i r m o l e c u l a r o r b i t a l s and a r e not p r o m o t e d , i s c a l l e d a s h a p e
r e s o n a n c e . T h e r e i s a n o t h e r type of r e s o n a n c e , the F e s h b a c h r e s o n a n c e s ,
in which the i n c i d e n t e l e c t r o n e x c i t e s the t a r g e t m o l e c u l e and i s t h e n i t s e l f
c a p t u r e d by the e x c i t e d s t a t e . We will s t a r t by d i s c u s s i n g s h a p e r e s o n a n c e s
only.
A s w e l l a s t h e r e s o n a n t r e a c t i o n s shown b y E q . (2. 1) t h e s a m e f i n a l
p r o d u c t s c a n be o b t a i n e d by a d i r e c t n o n - r e s o n a n t s c a t t e r i n g p r o c e s s ,
namely
e + N2(VJ = 0) - N 2 (v f = 0 or v f f 0) + e (2.2)
and t h i s d i r e c t p r o c e s s i n t e r f e r e s c o h e r e n t l y with the r e s o n a n t p r o c e s s .

T h e r e i s one way, h o w e v e r , by which the r e s o n a n t and d i r e c t p r o c e s s e s
can b e s e p a r a t e d in m o l e c u l e s , and t h i s i s a c h i e v e d by l o o k i n g at high
v a l u e s of v f , s i n c e t h e n t h e d i r e c t r e a c t i o n b e c o m e s n e g l i g i b l y s m a l l . In
a d i r e c t r e a c t i o n t h e s c a t t e r e d e l e c t r o n d o e s not s p e n d m u c h t i m e n e a r t h e
e1"7 = 2 i ' v A T ( 2 1 + 1 ) \t ( k r ) y°(cos8)
etc.
MOLECULAR FRAME-'
FIG. 18. A n g u l a r d i s t r i b u t i o n s of p a r t i a l w a v e s .
582 ' READ
t a r g e t m o l e c u l e , and i t s i n t e r a c t i o n with the n u c l e i of the m o l e c u l e m a y

r e s u l t in the e x c i t a t i o n of one o r two q u a n t a of v i b r a t i o n s , but i s unlikely
to give h i g h e r v i b r a t i o n a l e x c i t a t i o n . On the o t h e r hand, in a r e s o n a n t
r e a c t i o n the e l e c t r o n s p e n d s m u c h l o n g e r in the v i c i n i t y of the t a r g e t n u c l e i ,
s i n c e it i s c a p t u r e d to f o r m the r e s o n a n t s t a t e , and the e n v i r o n m e n t in which
the n u c l e i m o v e i s a l t e r e d to such an e x t e n t that l a r g e c h a n g e s in the v i b r a -
t i o n a l wave f u n c t i o n a r e quite p o s s i b l e . T h e r e f o r e , by looking at r e a c t i o n s
in which the change V; to v f i s l a r g e , one can u s u a l l y s u c c e e d in looking at
r e a c t i o n s which a r e n e a r l y p u r e l y r e s o n a n t . T h i s f a c t alone h a s m a d e it
p o s s i b l e to u s e the study of e l e c t r o n - m o l e c u l e r e s o n a n t c o l l i s i o n s a s a
s p e c t r o s c o p i c technique f o r studying the r e s o n a n t m o l e c u l e s . T h i s s i t u a t i o n
i s m a r k e d l y d i f f e r e n t f r o m t h a t in r e s o n a n t e l e c t r o n - a t o m c o l l i s i o n s , o r
r e s o n a n t n u c l e a r c o l l i s i o n s , in which the r e s o n a n t and n o n - r e s o n a n t p a r t s
cannot be s e p a r a t e d in t h i s way.
Now r e t u r n i n g to the e - N 2 r e a c t i o n , if the incident e l e c t r o n s have
m o m e n t u m f i ß j (in the z - d i r e c t i o n ) the incident plane wave can be w r i t t e n
a s exp (ikj . r ) , which can be expanded a s
exp (iSj - r ) = î* -J4ir{2$ + 1) j £ ( k ; r ) Y®(cos 0) (2. 3)

I
In o t h e r w o r d s the i n c i d e n t wave c a r r i e s a l l a n g u l a r m o m e n t a 1, and the

a n g u l a r d i s t r i b u t i o n s of the p a r t i a l w a v e s a r e a s shown in F i g . 18. None
of t h e m h a s the s y m m e t r y of the unfilled MO, and so none can be a b s o r b e d
by t h e N2 m o l e c u l e to m a k e N 2 . H o w e v e r , in s a y i n g t h i s we h a v e a s s u m e d
t h a t the i n c i d e n t z - d i r e c t i o n i s a l s o the d i r e c t i o n of o r i e n t a t i o n of the
i n t e r n u c l e a r a x i s . M o r e g e n e r a l l y , the m o l e c u l a r a x i s i s r o t a t e d through
t h e a n g l e s 9t with r e s p e c t to the l a b o r a t o r y a x i s .
Zmol
Now t h e p a r t i a l wave which h a s the a n g u l a r d i s t r i b u t i o n Y j ( 0 l a b , ф 1аЬ ) in the

l a b o r a t o r y f r a m e cam be e x p r e s s e d a s a s u m of d i s t r i b u t i o n s Y t (Ö m o l , Ф то1 ) w h e r e
the a n g l e s a r e now m e a s u r e d in the m o l e c u l a r f r a m e of r e f e r e n c e . In f a c t
Y F °(" L A B)= I У?(ПТ<Й) (2.4)

m
w h e r e 5? i s t h e t r a n s f o r m a t i o n f r o m Q l a b t o and w h e r e D i s the r o t a t i o n
m a t r i x . In o t h e r w o r d s , f r o m the point of view of the m o l e c u l e the incident
IAEA-SMR-12/26, 27 583
wave c o n t a i n s all a n g u l a r m o m e n t a Л and all c o m p o n e n t s m (where t h e s e

c o m p o n e n t s a r e m e a s u r e d along the z - a x i s of the m o l e c u l e ) . In f a c t it
c o n t a i n s p a r t i a l w a v e s such a s and Y] which can be a b s o r b e d to m a k e
the r e s o n a n t s t a t e . All the o t h e r p a r t i a l w a v e s , with the w r o n g s y m m e t r i e s ,
a r e s c a t t e r e d n o n - r e s o n a n t l y . The p r o b a b i l i t y of a b s o r b i n g a p a r t i a l wave
i s o b v i o u s l y a f u n c t i o n of the o r i e n t a t i o n
Soon a f t e r i t s f o r m a t i o n the N2 m o l e c u l e t h r o w s off i t s e x t r a e l e c t r o n ,
p e r h a p s in the d i r e c t i o n б of an e l e c t r o n d e t e c t o r . T h e s e outgoing p a r t i a l
w a v e s m u s t again have the s y m m e t r y of the MO. The p r o b a b i l i t y of d e t e c t i o n
at the angle в m u s t depend on both в and Ш.
To o b t a i n the a n g u l a r d i s t r i b u t i o n f o r the r e s o n a n t r e a c t i o n it i s n e c e s s a r y
to c o m b i n e the p r o b a b i l i t i e s of a b s o r b i n g and e m i t t i n g the r e l e v a n t p a r t i a l
w a v e s , and to i n t e g r a t e o v e r the p o s s i b l e o r i e n t a t i o n s Then we s h a l l
obtain the a n g u l a r d i s t r i b u t i o n а(в). C l e a r l y a ( 0 ) a l s o d e p e n d s on the
s y m m e t r y of the r e s o n a n t s t a t e , so p e r h a p s we s h a l l be able to d e d u c e
the s y m m e t r y f r o m m e a s u r e d a n g u l a r d i s t r i b u t i o n s .
We s h a l l go now, r a t h e r quickly, t h r o u g h t h e f o r m a l t r e a t m e n t of t h i s
a n g u l a r - c o r r e l a t i o n t h e o r y , in a s i m p l i f i e d t r e a t m e n t ; t h e f u l l t r e a t m e n t
h a s b e e n given by R e a d (1968) and A n d r i c k and R e a d (1971). T h i s t h e o r y
i s in e f f e c t a c o m b i n a t i o n of (i) the a n g u l a r - c o r r e l a t i o n t h e o r y d e v e l o p e d
b y n u c l e a r p h y s i c i s t s , (ii) the group t h e o r y which a p p l i e s to m o l e c u l e s ,
and (iii) the i r r e d u c i b l e t e n s o r m e t h o d developed by G r i f f i t h s (1962) and
others.
The s y m m e t r y c l a s s i f i c a t i o n of the e l e c t r o n i c s t a t e of the t a r g e t
m o l e c u l e can be r e p r e s e n t e d by | ď t )> w h e r e a j r e p r e s e n t s the i r r e d u c i b l e
r e p r e s e n t a t i o n to which the s t a t e b e l o n g s and a i i s the c o m p o n e n t of the
r e p r e s e n t a t i o n . S i m i l a r l y the r e s o n a n t and f i n a l m o l e c u l e s can be r e p r e -
s e n t e d by | a о ^ and |a f or f > r e s p e c t i v e l y . If we r e s t r i c t the t r e a t m e n t
to d i a t o m i c m o l e c u l e s , then all t h e e l e c t r o n i c s t a t e s have the s y m m e t r i e s
of the s p h e r i c a l h a r m o n i c s , and the d e s c r i p t i o n |a#)> could be r e p l a c e d
by the d e s c r i p t i o n |jPm^>. The i n i t i a l s t a t e of t a r g e t p l u s i n c i d e n t e l e c t r o n
can be w r i t t e n ^ m j l i j У and if Hj i s the o p e r a t o r which i n d u c e s the t r a n s i -
tion to the r e s o n a n t s t a t e then the m a t r i x e l e m e n t f o r the t r a n s i t i o n i s
O r m r I Hjl JP jiiij it j ^ o r m o r e b r i e f l y < m r | H a | m j ) > . S i m i l a r l y the m a t r i x
e l e m e n t f o r the b r e a k u p of the r e s o n a n t s t a t e m a y be w r i t t e n ^ m j k f | H ^ l ^ m ^
o r < m f j H 2 | m r >.
If t h e r e s o n a n t s t a t e h a s a l i f e t i m e т which i s v e r y s h o r t c o m p a r e d with
a r o t a t i o n a l p e r i o d then it a l s o n e c e s s a r i l y h a s an i n h e r e n t width Г which i s
m u c h l a r g e r than the s p a c i n g A E j b e t w e e n r o t a t i o n a l l e v e l s . In t h i s l i m i t ,
the i m p u l s e l i m i t , it can be shown that the d i f f e r e n t i a l c r o s s - s e c t i o n i s given
by
(2.5)
In o r d e r to e v a l u a t e < m r | H j | т ; )> it i s n e c e s s a r y to t r a n s f o r m the

p l a n e wave r e p r e s e n t a t i o n of the e l e c t r o n b e a m to i r r e d u c i b l e r e p r e -
s e n t a t i o n s of the s y m m e t r y point group of the m o l e c u l e . In the c a s e of
d i a t o m i c m o l e c u l e s t h i s w a s done in e f f e c t by E q s (2. 3) and (2.4) above.
584 ' READ
That is
m H m
< ' r r l i k i E i > = 1 ^ m r l ^ k m ^ m ^ D ^ K j - Z ^ ) (2.6)
4 mi
w h e r e t h e a r g u m e n t (Kj -» Z m o l ) r e p r e s e n t s the a n g l e s which d e s c r i b e t h e

r o t a t i o n f r o m the l a b o r a t o r y to m o l e c u l a r f r a m e . In t h e c a s e of n o n - l i n e a r
m o l e c u l e s t h i s r o t a t i o n i m p l i e s the t h r e e E u l e r a n g l e s , r a t h e r t h a n the two
a n g l e s n e e d e d f o r l i n e a r m o l e c u l e s . Now t h e W i g n e r - E c k a r t t h e o r e m s h o w s
t h a t the m a t r i x e l e m e n t •( ftmt | H j | i i m^ г т ^ c a n be s e p a r a t e d into a p a r t
which i s i n d e p e n d e n t of the c o m p o n e n t s rrij, m r and m x ( n a m e l y t h e r e d u c e d
m a t r i x e l e m e n t ) and a g e o m e t r i c a l f a c t o r which d o e s d e p e n d on t h e s e c o m p o -
nents (namely a Wigner 3-j coefficient). That is
< / r m r | H 1 | i i m A m 1 > = O r l k 1 I U i > ( ^ ^ ^ ) (2.7)
We m a y i n t e r p r e t t h e s e e q u a t i o n s a s f o l l o w s . E q u a t i o n (2.7) s a y s
t h a t the p a r t i a l w a v e l ^ m ^ c a n only be a b s o r b e d b y the t a r g e t >
to f o r m t h e r e s o n a n c e | j P r m r > if the W i g n e r c o e f f i c i e n t i s n o n - z e r o .
That is
X + f 1 = 7r (2.8)
with the s e l e c t i o n r u l e s w h i c h t h i s i m p l i e s . E q u a t i o n (4) g i v e s t h e p r o b a b i l i t y

of f i n d i n g l ^ m j ) - in the i n c i d e n t b e a m . S i m i l a r l y in the o u t g o i n g p a r t of t h e
r e a c t i o n ( i . e . t h e " e x i t c h a n n e l " , to d i s t i n g u i s h it f r o m t h e i n i t i a l " e n t r a n c e
c h a n n e l " ) one h a s
Tt = 7f +12 (2.9)
1 j and f 2 a r e h e r e the r e s o n a n t p a r t i a l w a v e s in t h e e n t r a n c e and e x i t

channels.
B y c o m b i n i n g e q u a t i o n s (2.5), (2.6) and (2.7), and i n t e g r a t i n g o v e r
a l l p o s s i b l e o r i e n t a t i o n s of t h e t a r g e t m o l e c u l e , and u s i n g s o m e R a c a h
a l g e b r a to s u m o v e r v a r i a b l e s , we c a n now d e r i v e an e x p r e s s i o n f o r ст(0),
namely
о (в) ~ ) A k P k ( c o s 6) (2.10)
where
Ak (Zk+l)^ 0 0J yQ 0 QJ N
X R ( i m m , R i m , i m 1
( m 2 Д N ) i i W r r ( i i A 4 r ; ) " '
X R ( t { m f f 2 m 2 t i m r ) * R (£fm}i ' m ^ l r m ' ) (2.11)

IAEA-SMR-12/26, 27 585
w h e r e t h e s u m m a t i o n i s o v e r the u n o b s e r v e d c o m p o n e n t s m ^ n i j , mj.,
and m f , and i s a l s o o v e r ^ т - ^ т ^ т ^ ' т ^ . T h e R ' s a r e a m p l i t u d e s
which depend on the d e t a i l s of r a d i a l wave f u n c t i o n s e t c .
It o f t e n h a p p e n s t h a t the e n t r a n c e c h a n n e l c o n t a i n s only one p a r t i a l
wave of a p p r e c i a b l e a m p l i t u d e , a l l the r e s t b e i n g n e g l i g i b l e . T h i s i s a l s o
t r u e of the exit c h a n n e l . The r e a s o n s f o r t h i s will be d i s c u s s e d l a t e r .
It m e a n s t h a t t h e r e i s only one value f o r and jPa and f o r f 2 a n d In
t h i s c a s e t h e r e a r e s o m e s e l e c t i o n r u l e s hidden in E q . (2.11), n a m e l y
к i s an even n u m b e r only (2.12)
(or e l s e the f i r s t two W i g n e r c o e f f i c i e n t s would be z e r o ) and

k
max = m i n i m u m ( 2 ^ , 2j>2) (2.13)
(or e l s e s o m e o r a l l of the W i g n e r c o e f f i c i e n t s would be z e r o ) .

The s e l e c t i o n r u l e s can be s u m m a r i z e d by a v e c t o r p i c t u r e
w h e r e the h i g h e s t o r d e r of L e g e n d r e p o l y n o m i a l in cr(0) i s d e t e r m i n e d by
the s m a l l e r of JPJ and l 2 .
In the c a s e of n o n - l i n e a r m o l e c u l e s t h e d e r i v a t i o n of cr(0) i s m o r e
c o m p l i c a t e d : one m u s t t r a n s f o r m f r o m the s p h e r i c a l group r e p r e s e n t a t i o n s
Yj to i r r e d u c i b l e r e p r e s e n t a t i o n s of the group to which the m o l e c u l e b e l o n g s .
T h i s a l s o i n v o l v e s r e p l a c i n g s o m e W i g n e r c o e f f i c i e n t s by t h e i r a n a l o g u e s
f o r the c r y s t a l l o g r a p h i c point g r o u p s .
Some c a l c u l a t e d a n g u l a r d i s t r i b u t i o n s a r e shown in F i g . 19.
To r e t u r n to the N"2 r e s o n a n c e , the r e s o n a n t s t a t e h a s the s y m m e t r y
of the l a s t Tg2p o r b i t a l . T h i s h a s a n g u l a r m o m e n t u m 1 about the i n t e r -
n u c l e a r a x i s ( t h e r e f o r e m r = 1), and t z m u s t be even ( b e c a u s e of the g e r a d e
s y m m e t r y ) . T h e r e f o r e t h i s s y m m e t r y i s s p a n n e d by Y^ 1 , Y^ 1 , Y^1 e t c . ,
a s was c l e a r f r o m F i g . 1 8 . The i n i t i a l and t a r g e t m o l e c u l e s a r e
both in Eg s t a t e s , and t h e r e f o r e S i = m ; = jřf = m f = 0. The s e l e c t i o n r u l e s
t h e r e f o r e give t h a t (l x , m x ) = (jř2, m 2 ) = (2, ± 1 ) o r (4, ± 1 ) , o r (6, ± 1 ) e t c .
The p a r t i a l w a v e s (2, ± 1 ) a r e m u c h s t r o n g e r than the r e s t . T h i s can
be u n d e r s t o o d q u a l i t a t i v e l y by c o n s i d e r i n g t h e e f f e c t i v e r a d i a l p o t e n t i a l
s e e n by an i n c i d e n t e l e c t r o n . T h i s p o t e n t i a l i s m a d e up of an a t t r a c t i v e
p a r t due to the t a r g e t m o l e c u l e , and a r e p u l s i v e c o n t r i b u t i o n f r o m t h e
c e n t r i f u g a l p o t e n t i a l , a s shown in F i g . 20. The c o m b i n a t i o n p r o d u c e s a
586 ' READ
F I G . 19. Calculated angular distributions, ( a ) p o ( 2 ' , d o < 2 ) , f o ( 2 ' , and f ® ' 1 ^ ; (b) р7г(У, d u t 1 ' , f/ 1
',
and f i r ^ ; (с) dó(W, f ó ^ y , f ó ( ® , and f ® ( 2 ' . AU n o r m a l i z e d t o 1 a t 0 ° ( f r o m Read, 1968).
FIG,20. Effective potential.

IAEA-SMR-12/26, 27 587
c e n t r i f u g a l b a r r i e r , which i s one r e a s o n f o r the e x i s t e n c e of the r e s o n a n c e .

T h i s b a r r i e r t r a p s the e l e c t r o n in the r e s o n a n t s t a t e and s t o p s the l i f e t i m e
f r o m b e i n g too s h o r t . The b a r r i e r also h i n d e r s the incident e l e c t r o n , and
if the b a r r i e r i s too high the incident e l e c t r o n cannot p a s s t h r o u g h it to
f o r m the r e s o n a n c e . T h i s i s why the h i g h e r p a r t i a l w a v e s a r e i n e f f e c t i v e .
The N2 r e s o n a n c e i s t h e r e f o r e f o r m e d by the (2, ± 1 ) p a r t i a l w a v e s .
T h e e x p e c t e d a n g u l a r d i s t r i b u t i o n i s one of t h o s e shown in F i g . 19 (the one
m a r k e d d ^ 1 ' ) and t h i s a g r e e s with the o b s e r v e d d i s t r i b u t i o n s shown in
F i g . 17. The h y p o t h e s i s of 7rg - s y m m e t r y f o r the r e s o n a n t s t a t e i s t h e r e f o r e
verified.
0 (<кэ)
FIG. 21. A n g u l a r d i s t r i b u t i o n s for r e s o n a n t e - C O , s c a t t e r i n g .

(a) D i f f e r e n t i a l c r o s s - s e c t i o n at i n c i d e n t e n e r g y 3 . 6 e V and e n e r g y loss of 172 m e V ; c u r v e o b t a i n e d as
least-squares fit; (b) D i f f e r e n t i a l c r o s s - s e c t i o n a t i n c i d e n t e n e r g y 3 . 6 e V , e n e r g y loss 83 m e V , least-
squares fit (from Andrick and Read, 1971).
588 ' READ
H e r e we h a v e gone through the t h e o r y of r e s o n a n t a n g u l a r d i s t r i b u t i o n s

a s though it applied to shape r e s o n a n c e s only. In f a c t it i s m o r e g e n e r a l
than t h i s , and can be applied f o r e x a m p l e to F e s h b a c h r e s o n a n c e s in which
the incident e l e c t r o n e x c i t e s the t a r g e t m o l e c u l e and i s then c a p t u r e d by
the e x c i t e d s t a t e . L a t e r on we s h a l l s e e t h r e e e x a m p l e s like t h i s in Щ .
The t h e o r y a l s o a p p l i e s to v i b r a t i o n a l e x c i t a t i o n s . In d i a t o m i c m o l e c u l e s
t h e v i b r a t i o n a l wave f u n c t i o n s a r e all t o t a l l y s y m m e t r i c , and t h e v i b r o n i c
( v i b r a t i o n a l - e l e c t r o n i c ) s y m m e t r y i s t h a t of the e l e c t r o n i c s t a t e , but in
n o n - l i n e a r m o l e c u l e s t h e v i b r o n i c s y m m e t r y d e p e n d s a l s o on the m o d e of
v i b r a t i o n . The s y m m e t r y c l a s s i f i c a t i o n s which m u s t be used when applying
the a n g u l a r d i s t r i b u t i o n t h e o r y a r e t h e r e f o r e t h e v i b r o n i c s y m m e t r i e s .
We s h a l l deal with t h e q u e s t i o n of r o t a t i o n a l s y m m e t r i e s l a t e r : they do not
a p p e a r in the p r e s e n t t r e a t m e n t b e c a u s e we have a s s u m e d that the r e s o n a n t
s t a t e s a r e m u c h w i d e r than the r o t a t i o n a l s p a c i n g (so t h a t t h e r e i s no r e s o n a n t
r o t a t i o n a l s t r u c t u r e ) and we a r e also i m p l i c i t l y s u m m i n g and a v e r a g i n g o v e r
the f i n a l and i n i t i a l r o t a t i o n a l s t a t e s , when we a v e r a g e o v e r m o l e c u l a r
orientations.
A nice e x a m p l e of the i n f l u e n c e of v i b r a t i o n a l s y m m e t r i e s i s t h a t of
the CO2 r e s o n a n c e which a p p e a r s in e - C 0 2 c o l l i s i o n s at about 3.5 eV.
F i g u r e 21 s h o w s s o m e a n g u l a r d i s t r i b u t i o n s t a k e n f r o m A n d r i c k and R e a d
(1971), and F i g . 22 s h o w s the e x p e c t e d p a r t i a l w a v e s . The e x t r a e l e c t r o n
t e n d s to bend the r e s o n a n t m o l e c u l e , which u p s e t s i t s s y m m e t r y and a l l o w s
TARGET
* • [Kionj'dn,)'
MOLECULE
's:
RESONANT
TARGET M 0 ' S + 2 n
STATE С
( a )
F I N A L STATE
EITHER • • • -
SYM. STRETCHING MODE 1100)
OR ^ . }
BENOING MODE
(010)
OR « . • »
ASYMMETRIC STRETCHING MODE
lb)
FIG.22. Partial waves to be e x p e c t e d , (a) ( i , m ) = (1, ±1), (3, ±1) + (0,0), because symmetry
is n o t e x a c t l y П ц . ( b ) for s y m m e t r i c s t r e t c h i n g m o d e ( { , m ) = ( 1 , ± 1 ) , ( 3 , ± 1 ) , . . . ( 0 , 0 ) , a g a i n , for b e n d i n g
m o d e ( i , m ) = ( 0 , 0 ) , ( 2 , 0), ( 2 , ± 2 ) , and for t h e a s y m m e t r i c s t r e t c h i n g m o d e t h e r e is n o F r a n c k - C o n d o n
o v e r l a p with the resonant state.
I A E A - S M R - 1 2 / 2 6 , 27 589
f o r p a r t i a l w a v e s such a s (0, 0). O t h e r w i s e the 7ru s y m m e t r y would only allow

m = + 1, S = odd. When the f i n a l m o l e c u l e i s l e f t in a s y m m e t r i c v i b r a t i o n a l
m o d e then the exit c h a n n e l c o n t a i n s the s a m e p a r t i a l w a v e s as the e n t r a n c e
c h a n n e l , and the d a t a have b e e n i n t e r p r e t e d in t h i s way. On the o t h e r hand,
when a b e n d i n g v i b r a t i o n a l m o d e i s e x c i t e d , the o v e r a l l (vibronic) s y m m e t r y
of the m o l e c u l e i s changed. It now h a s u s y m m e t r y and i 2 h a s to be even.
The o b s e r v e d a n g u l a r d i s t r i b u t i o n s a l s o c h a n g e .
One s e e s t h e r e f o r e that the a n g u l a r d i s t r i b u t i o n s a r e d e t e r m i n e d by the
v i b r a t i o n a l and e l e c t r o n i c s y m m e t r i e s . A slight change in v i b r a t i o n a l e n e r g y
c a u s e s a p r o f o u n d change in the outgoing p a r t i a l w a v e s .
3. D E T E R M I N A T I O N O F P O T E N T I A L FUNCTIONS
E x p e r i m e n t a l d a t a on e l e c t r o n - m o l e c u l e c o l l i s i o n s can o f t e n be u s e d
to d e t e r m i n e the p o t e n t i a l f u n c t i o n s of the r e s o n a n t s t a t e s . We s h a l l show
t h i s on c o n s i d e r i n g a r a t h e r s i m p l e type of a n a l y s i s , and will then go on
to d i s c u s s the c o m p l i c a t i o n s which can a r i s e .
INTERNUCLEAR DISTANCE R
FIG. 23. S k e t c h of v i b r a t i o n a l l e v e l s a n d p o t e n t i a l f u n c t i o n s .
590 ' READ
C o n s i d e r r e s o n a n t e - H 2 c o l l i s i o n s as an e x a m p l e .
e + H 2 ( V i ) - H j ( v r ) - e + H 2 (v f )
In F i g . 23 s o m e v i b r a t i o n a l l e v e l s and p o t e n t i a l f u n c t i o n s a r e s k e t c h e d f o r
such a t r a n s i t i o n . Once again the r o t a t i o n a l s t a t e s a r e a s s u m e d to be not
r e s o l v e d ( r o t a t i o n a l t r a n s i t i o n s will be d i s c u s s e d l a t e r ) .
F o r m a n y r e s o n a n t r e a c t i o n s the c r o s s - s e c t i o n f a c t o r s into two p a r t s ,
one which d e p e n d s on a n g l e s and is p u r e l y g e o m e t r i c a l in c h a r a c t e r (this
i s the p a r t we w e r e d i s c u s s i n g e a r l i e r ) and a n o t h e r p a r t which d e p e n d s on
the d e t a i l s of the wave f u n c t i o n s but i s independent of a n g l e s (this w a s
contained in the f a c t o r s R which a p p e a r e d in Eq, (2.11)). It i s t h i s s e c o n d
p a r t which we want to d i s c u s s now. It d e p e n d s on both the e l e c t r o n i c
and v i b r a t i o n a l wave f u n c t i o n s .
In a s i m p l e photon a b s o r p t i o n p r o c e s s b e t w e e n v i b r a t i o n a l l e v e l s Vj
and v r (of two d i f f e r e n t e l e c t r o n i c s t a t e s jPt and jPr ) the d e p e n d e n c e of the
a b s o r p t i o n c r o s s - s e c t i o n on v ; and v r i s given b y the F r a n c k - C o n d o n
overlap factor
CO
qfejVj - e r v r ) = | J ~ R ) * <|>(ervr; R ) d R [Z (3.1)

0
w h e r e R i s the i n t e r n u c l e a r d i s t a n c e and ф i s a v i b r a t i o n a l wave function.

S i m i l a r l y f o r m a n y r e s o n a n t e l e c t r o n s c a t t e r i n g p r o c e s s e s the c r o s s - s e c t i o n
f o r f o r m i n g the r e s o n a n t s t a t e i s p r o p o r t i o n a l to qťejVj e r v r ) and the p r o b a -
bility of i t s d e c a y i n g to v i b r a t i o n a l l e v e l v f of the e l e c t r o n i c s t a t e e f i s
p r o p o r t i o n a l to q ( e r v r - e f v f ) . F u r t h e r m o r e , if the r e s o n a n t v i b r a t i o n a l
l e v e l v r h a s a m e a n e n e r g y E r and a n a t u r a l width Г г , then the p r o b a b i l i t y
of it b e i n g f o r m e d when the incident e n e r g y i s E h a s the B r e i t - W i g n e r f o r m
{(E - E r ) 2 + i Г 2 }" 1 . T h e r e f o r e the o v e r a l l c r o s s - s e c t i o n h a s the f o r m
/T-. \ Q (ejVj ^ e. v r ) q (e r v r - e f v f ) .„ . .
g (b; e j v i - er vr - e f v f ) = g 4 ' ' \ ^ (3.2)
The f a c t o r g d e p e n d s on the e l e c t r o n i c wave f u n c t i o n s , but we s h a l l a s s u m e

that it i s n e a r l y c o n s t a n t o v e r the o b s e r v e d r a n g e s of e n e r g i e s of the r e s o n a n t
and f i n a l s t a t e s . The d e r i v a t i o n of Eq. (3.2) and the a s s u m p t i o n s i m p l i c i t
in it have b e e n d i s c u s s e d in the r e v i e w by B a r d s l e y and Mandl (1968).
E q u a t i o n (3.2) can be u s e d to find p o t e n t i a l f u n c t i o n s of r e s o n a n t s t a t e s .
F o r e x a m p l e , F i g . 11 s h o w s s o m e m e a s u r e m e n t s in I ^ . The p o t e n t i a l
f u n c t i o n of the H 2 ground s t a t e i s known, and by m a k i n g v a r i o u s g u e s s e s of
the p o t e n t i a l f u n c t i o n of the r e s o n a n t s t a t e one can t r y to r e p r o d u c e all the
peak i n t e n s i t i e s shown in t h e f i g u r e . In f a c t t h i s g u e s s i n g w a s done by a
c o m p u t e r p r o g r a m which u s e d a l e a s t - s q u a r e s m e t h o d . In t h i s p r o g r a m
the p o t e n t i a l f u n c t i o n of the ground e l e c t r o n i c s t a t e was a p p r o x i m a t e d by a
Morse function
E(R) = E 0 + hcD [1 - exp (-ß(R - R £ )) f (3.3)

IAEA-SMR-12/26, 27 5 9 1
2
ZgISERIES a )
П 2 3
R(&)
FIG.24. P o t e n t i a l c u r v e s f o r H 2 - s t a t e s ( b r o k e n c u r v e s ) g i v i n g best f i t ( C o m e r a n d R e a d , 1 9 7 1 ) . Corresponding

c u r v e s for s o m e H 2 - s t a t e s ( f u l l ) a c c o r d i n g t o S h a r p ( 1 9 6 9 ) . E n e r g y s c a l e t a k e n w i t h r e s p e c t to b o t t o m of g r o u n d -
state potential curve.
T h i s a p p r o x i m a t i o n was a l s o u s e d f o r the r e s o n a n t s t a t e s . The c u r v e s

obtained f o r t h i s r e s o n a n t s t a t e (called " s e r i e s a") and f o r two o t h e r
r e s o n a n t s t a t e s , a r e shown in F i g . 24.
Some d e t a i l s of the t h r e e s e r i e s called a, b and с a r e shown in T a b l e I.
We will d i s c u s s t h e m l a t e r ; h e r e we s h a l l l i s t s o m e f a c t s about t h e m .
S e r i e s a h a s b e e n o b s e r v e d by s e v e r a l a u t h o r s . I t s p a r e n t s t a t e (i. e.
the e x c i t e d s t a t e of H 2 which i s able to c a p t u r e an e x t r a e l e c t r o n , with a
binding e n e r g y of about 0.5 eV, to m a k e the r e s o n a n t s t a t e ) i s the с 3 Пц s t a t e .
It h a s a l s o b e e n found t h e o r e t i c a l l y by E l i e z e r et al. (1967). The m e a s u r e d
a n g u l a r d i s t r i b u t i o n s a r e i s o t r o p i c , which shows that it m u s t have 2 Eg
s y m m e t r y (also a s found t h e o r e t i c a l l y ) .
S e r i e s b w a s o b s e r v e d only by C o m e r and R e a d (1971). T h e r e a s o n i s t h a t

it h a s an e q u i l i b r i u m i n t e r n u c l e a r d i s t a n c e which i s r a t h e r l a r g e (like i t s p a r e n t
s t a t e , В 1 Ец), and t h e r e f o r e i t s v i b r a t i o n a l l e v e l s have the g r e a t e s t F r a n c k -
Condon o v e r l a p with high v i b r a t i o n a l l e v e l s of the e l e c t r o n i c ground s t a t e .
T h e r e f o r e it i s only o b s e r v e d when v f i s l a r g e . Some m e m b e r s of s e r i e s b
a r e shown in the b o t t o m l e f t - h a n d c o r n e r of F i g . 11. The s t a t e h a s s y m m e t r y
2
Eg again. T h i s s t a t e h a s not b e e n r e p r o d u c e d t h e o r e t i c a l l y yet.
СЛ
CD
to
T A B L E I. SOME Щ RESONANCES
[ f r o m C o m e r and R e a d (1971) and J o y e z et al. (1973) ]
Series aa b с da
era +
2
Symmetry r +g
4 4
3
Parent 3
c nu c \ , a £+ с3Пи
M o l e c u l a r orbitals (ogls)(,ru2p)2 (Ogls) (o u ls) 2 (Ogls) (тг и 2р) ( o g 2 s ) (ogls)(7Tu2p)(ouls)
MÄ) 0.97 ±0.01b 1.175 i 0.01b 0.97 ±0.01b 0.97
a(eV) 0.345 i 0.015 0.19 ±0.015 0.28 ± 0.025 M 0.345

bd
b(eV) 0.0135 ± 0.003 0.005 i 0.003 0.015 ± 0.005 0.0135
Eo(eV)c 11.40 11.11 11.45 11.40
g / F 2 ,(A2) 0.3(H2), 0.35(D2) 0.01
f o . 045 ( H 2 )
r(eV)
* \ 1_0.03 (D2)
0.03
Exit c h a n n e l s x'Sg (H2, D2) x'ZgCHz) x'rgtDz) B'S^H,)
b3zj(H2)? b3E+(H2)î
u
A further series in this energy r e g i o n , c a l l e d series II has b e e n observed in t h e x and В e x i t c h a n n e l s in H 2 . T h e Morse p a r a m e t e r s r e f e r to H2 for series a ,
b , and d , and D 2 for series c .
a
Previously c a l l e d series I. T h e possibility exists t h a t series с and d are i d e n t i c a l with s y m m e t r y П и .
b Error d e t e r m i n e d from l e a s t - s q u a r e s fits.
c
The e n e r g y of the m i n i m u m point of the r e s o n a n c e p o t e n t i a l c u r v e with respect ro the m i n i m u m point of the ground s t a t e p o t e n t i a l c u r v e ,
d D2 parameters.
IAEA-SMR-12/26, 27 593
i .. ' 20
й 1 !
v^..;-:'? 40°
85
11-5 12-0 12 5
Collision energy teV)
FIG.25. Resonant e x c i t a t i o n in D z , w i t h A v = 7 . The arrows show t h e positions of series c .
S e r i e s c. T h i s w a s s e e n in s o m e of t h e e x p e r i m e n t s on
e - D 2 s c a t t e r i n g . F i g u r e 25 shows s o m e r e s u l t s . S e r i e s с i s not v e r y
a p p a r e n t h e r e , but will be s e e n m u c h m o r e c l e a r l y in one of the following
f i g u r e s . T h i s s e r i e s d o e s not have an i s o t r o p i c a n g u l a r d i s t r i b u t i o n —
F i g . 26 s h o w s t h i s . In f a c t the s t a t e h a s s y m m e t r y 2 П и — but again the
r e a l e v i d e n c e f o r t h i s will c o m e l a t e r . It a l s o h a s not b e e n found t h e o r e t i c a l l y
yet.
One a s s u m p t i o n which i s i m p l i c i t in E q . (3.2) i s t h a t e a c h r e s o n a n t l e v e l
e f v r h a s a d e f i n i t e e n e r g y E t , and that this e n e r g y i s independent of the way
in which the s t a t e i s o b s e r v e d . A c t u a l l y t h i s i s not t r u e , a s can be s e e n
f r o m F i g . 27. The p o t e n t i a l f u n c t i o n s should r e a l l y be r e p r e s e n t e d a s f u z z y
l i n e s , of width Г. The s t a t e s er vr a r e not s t a t i o n a r y s t a t e s , but have a
lifetime
r = ft/F (3.4)
F o r e x a m p l e s e r i e s a h a s Г 4 16 m e V and t h e r e f o r e т ^ 4 Х 10" 14 s. But

the m e a s u r e d v i b r a t i o n a l e n e r g y s p e c t r u m s h o w s t h a t hy = 0.345 eV, which
m e a n s t h a t the v i b r a t i o n a l p e r i o d i s 2 X 10~14 s. In t h i s s i t u a t i o n , in which
5 9 4 ' READ
FIG. 26. A n g u l a r d i s t r i b u t i o n of series c .
the r e s o n a n t s t a t e l i v e s f o r only about two v i b r a t i o n a l p e r i o d s , it i s not

s u r p r i s i n g that the a p p a r e n t r e s o n a n t e n e r g y d e p e n d s on the d e c a y m o d e
which i s b e i n g o b s e r v e d . N e v e r t h e l e s s t h e r e a s o n a b l y good a g r e e m e n t
b e t w e e n the o b s e r v e d p e a k i n t e n s i t i e s and t h o s e c a l c u l a t e d f r o m E q . (3.2)
l e a d s one to hope t h a t the d e d u c e d p o t e n t i a l c u r v e s a r e r e a s o n a b l y a c c u r a t e .
T h e r e a r e o t h e r e x a m p l e s in which the r e s o n a n t s t a t e h a s a l i f e t i m e
which i s s h o r t e r than a v i b r a t i o n a l p e r i o d . F o r e x a m p l e , the N 2 r e s o n a n c e s
at 2.3 eV a r e like t h i s . E q u a t i o n (3.2) cannot be u s e d t h e n , and the p o t e n t i a l
f u n c t i o n f o r t h e r e s o n a n t s t a t e can only be found by a m o r e c o m p l e t e a n a l y s i s .
F i g u r e 28 shows how an a n a l y s i s was m a d e f o r N2 by B i r t w i s t l e and
H e r z e n b e r g (1971). T h e y u s e d the " b o o m e r a n g " m o d e l in which a f t e r the
i n i t i a l f o r m a t i o n of the N 2 s t a t e the n u c l e i s t a r t to move a p a r t and the s t a t e
s t a r t s to d e c a y : if the s t a t e s u r v i v e s f o r a long enough t i m e f o r t h e n u c l e i
to r e a c h the r i g h t - h a n d s i d e of the p o t e n t i a l f u n c t i o n then the n u c l e i a r e
r e f l e c t e d and s t a r t to m o v e t o g e t h e r again (the " b o o m e r a n g " ) but the s t a t e
I A E A - S M R - 1 2 / 2 6 , 27 595
EXIT CHANNEL ENERGY POSITIONS OF OBSERVED FEATURES

i i i i i i i i i i i i i i i i i i i i i i i i i
v = 13 1 1
v = 12 1 1
»=11
Il M
v=10
II 1 1 1 1
v=9 1 1 1 1 1
v=8 I I 1 1 1 1
v 7
x's; = 1 1
V=6 1 1
v=5
1 1 1 1
v=4 1 1 1 1
v=3
v=2
v=1
v =0 1 1 1 1 1 1
1 1 1 1 1 I ( I ( 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
11.5 12 12.5 13
COLLISION ENERGY
FIG.27. M e a s u r e d r e s o n a n c e e n e r g i e s in e - H 2 scattering.
i s m o s t u n l i k e l y to live long enough to m a k e m o r e than one r e f l e c t i o n . The

a p p a r e n t e n e r g y of t h e r e s o n a n t s t a t e i s then v e r y d e p e n d e n t on the o b s e r v e d
v i b r a t i o n a l change.
A n o t h e r , m o r e e m p i r i c a l , m e t h o d h a s b e e n u s e d to find p o t e n t i a l c u r v e s
f o r r e s o n a n t s t a t e s of s o m e m o l e c u l e s . T h i s c o n s i s t s in u s i n g B a d g e r ' s r u l e ,
which gives t h a t
w h e r e k e = 4тг 2 ^ 2 с 2 и| i s the f o r c e c o n s t a n t , ц i s the r e d u c e d m a s s , с i s

the v e l o c i t y of light and R u e i s the v i b r a t i o n a l e n e r g y s p a c i n g of the r e s o n a n t
s t a t e . Cjj and dy a r e e m p i r i c a l c o n s t a n t s which a r e c h a r a c t e r i s t i c of all
d i a t o m i c m o l e c u l e s which c o n s i s t of one a t o m in the i - t h long r o w and one
in the j - t h long r o w of the p e r i o d i c s y s t e m . F o r e x a m p l e , f o r 0 2 we have
i = j = 1 and the e m p i r i c a l c o n s t a n t s a r e с = 1.86 X 10 5 d y n e / c m and d = 0 . 6 8 0 Â .
With t h e s e v a l u e s the e r r o r in R e i s l e s s t h a n about 0.05 Â. B o n e s s and
Schulz u s e d t h e i r m e a s u r e d value of we f o r O j to d e d u c e R g = 1.377 Â i n
t h i s way.
5 9 6 ' READ
NUCLEAR SEPARATION R
FIG. 28. B o o m e r a n g m o d e l of n u c l e a r w a v e f u n c t i o n in t h e N 2 ion w h i c h suggests t h e c a l c u l a t i o n w i t h

v a r i a b l e Г. T h e s c h e m a t i c m o d e l has b e e n discussed by H e r z e n b e r g ( 1 9 6 8 ) ; i t is b a s e d on t h e a s s u m p t i o n
t h a t t h e m a g n i t u d e and R - d e p e n d e n c e of T(R) a r e such t h a t o n l y a s i n g l e o u t g o i n g a n d a s i n g l e r e f l e c t e d
w a v e m a t t e r ( f r o m Birtwistle a n d H e r z e n b e r g , 1971).
4. R O T A T I O N A L T R A N S I T I O N S IN R E S O N A N C E REACTIONS
In any e l e c t r o n - m o l e c u l e collision the t a r g e t m o l e c u l e s have a r a n g e

of v a l u e s of the r o t a t i o n a l quantum n u m b e r and the f i n a l m o l e c u l e s m a y
be l e f t in v a r i o u s r o t a t i o n a l s t a t e s J f , which m e a n s that the change in
rotational energy
Д Е , = B . {J F (J F + 1) - JJTJJ + 1 ) } (4.1)
m a y t a k e m a n y d i f f e r e n t v a l u e s . H o w e v e r , in the e x p e r i m e n t s d e s c r i b e d
so f a r the e n e r g y width A E of the incident b e a m h a s b e e n t y p i c a l l y in t h e
r a n g e 30 to 50 m e V , and the e n e r g y r e s o l u t i o n of the a n a l y s e r s f o r the
I A E A - S M R - 1 2 / 2 6 , 27 597
s c a t t e r e d e l e c t r o n s h a s b e e n about the s a m e , and s i n c e f o r m o s t m o l e c u l e s

A E j i s t y p i c a l l y 4 20 m e V it h a s not been p o s s i b l e to r e s o l v e c l e a r l y the
different transitions J ; J f . T h i s i s why I have i g n o r e d the r o t a t i o n a l
s t r u c t u r e so f a r .
The v a l u e s of A E j a r e l a r g e s t f o r the l i g h t e s t m o l e c u l e , H 2 , and
r e c e n t l y we have b e e n able to r e s o l v e i t s r o t a t i o n a l s t r u c t u r e : F i g . 10
s h o w s an e n e r g y - l o s s s p e c t r u m f o r an incident e n e r g y of 11.07 eV. H e r e
t h e s e l e c t o r and a n a l y s e r had r e s o l u t i o n s of about 12 m e V , and the o v e r a l l
e n e r g y r e s o l u t i o n of the s e l e c t o r - a n a l y s e r s y s t e m w a s 17 m e V . S e v e r a l
r o t a t i o n a l t r a n s i t i o n s can be c l e a r l y s e e n . The s t r o n g e s t t r a n s i t i o n i s
J j = 1 J f = 3 , s i n c e 67% of the t a r g e t m o l e c u l e s have J ; = 1. The v e r y
l a r g e c e n t r a l p e a k c o n t a i n s all t h e t r a n s i t i o n s f o r which Jj = J f .
The a n g u l a r d i s t r i b u t i o n t h e o r y of section 2 m u s t be m o d i f i e d when
d i s c r e t e r o t a t i o n a l l e v e l s a r e c o n s i d e r e d . We s h a l l not go into the d e t a i l s
of t h e m o d i f i e d t h e o r y (these d e t a i l s can be found in R e a d and A n d r i c k , 1971),
but d i s c u s s the new s e l e c t i o n r u l e s which a r e p r e s e n t in r o t a t i o n a l t r a n s i t i o n s .
C o n s i d e r a s an e x a m p l e a h o m o n u c l e a r d i a t o m i c m o l e c u l e such a s H 2
in which the e l e c t r o n i c s t a t e s of the i n i t i a l and f i n a l m o l e c u l e s both have
J
Eg s y m m e t r y . Suppose t h a t the i n i t i a l and f i n a l r o t a t i o n a l quantum n u m b e r s
a r e Jj and J f , r e s p e c t i v e l y , and s u p p o s e t h a t the r o t a t i o n a l q u a n t u m n u m b e r
of the r e s o n a n t s t a t e , e x c l u d i n g the e l e c t r o n spin, i s J r . We want to know
s o m e t h i n g about the a n g u l a r d i s t r i b u t i o n and the s e l e c t i o n r u l e s f o r the
scattering p r o c e s s J; Jr J{.
In s e c t i o n 2 we a s s u m e d t h a t the width Г of the r e s o n a n t s t a t e i s l a r g e r
than the e n e r g y s p a c i n g s b e t w e e n the r o t a t i o n a l l e v e l s J r (i. e. the i m p u l s e
a p p r o x i m a t i o n ) : t h i s m e a n s of c o u r s e that the l e v e l s J r a r e u n o b s e r v a b l e ,
and i n d e e d do not e x i s t a s r o t a t i o n a l s t a t e s . In t h e p r e s e n t d i s c u s s i o n we
s t a r t with a d i f f e r e n t a s s u m p t i o n (which i s r e f e r r e d to a s t h e " l o n g - l i f e t i m e
l i m i t " ) , n a m e l y that the l i f e t i m e (т = ft/Г) of the r e s o n a n t s t a t e i s g r e a t e r
t h a n , o r of the o r d e r of, the r o t a t i o n a l p e r i o d . T h i s a l s o m e a n s that Г 4
the s p a c i n g b e t w e e n the l e v e l s J r , and that t h e s e l e v e l s can be r e s o l v e d ,
in p r i n c i p l e . The t h e o r y p e r t a i n i n g to t h i s l i m i t h a s b e e n given by B ö t t c h e r
and R e a d (1973), but we can e s t a b l i s h the r e l e v a n t s e l e c t i o n r u l e s without
going into the d e t a i l s of the t h e o r y .
If, a s in s e c t i o n 2, JPJ and i 2 a r e the a n g u l a r m o m e n t a of the p r i n c i p a l
p a r t i a l w a v e s in the e n t r a n c e and exit c h a n n e l s , then one h a s f o r r e s o n a n t
s c a t t e r i n g in H 2 (in the l o n g - l i f e t i m e l i m i t )
J + = J = J +
1 h r f h <4-2'
2 +
F o r e x a m p l e , if the r e s o n a n t s t a t e h a s s y m m e t r y Kg, then one would e x p e c t
JP-J = JP2 = 0, and t h e r e f o r e J ; = J r = J f . This would m e a n that the o b s e r v e d
v a l u e s of
A J = J f - Jj (4.3)
2
would all be z e r o . On the o t h e r hand, for a r e s o n a n t s t a t e of flu s y m m e t r y
one would have = f2 = and A J = 0 or ± 2. T h e r e f o r e , by o b s e r v i n g
which t r a n s i t i o n s J j -* Jf a r e p r e s e n t , one can help to e s t a b l i s h the s y m m e t r y
of the r e s o n a n t s t a t e .
598 ' READ
1—i 1 1 1 1 r—
— SERIES A
SERIES С
— SERIES A'
I :• Av = i
I 25°
Н /
:'• \ *
J w
Av = 4
90°
AV = e
25°
• Л Л А *
Av = 6
90°
;
i - L ' - i '
11.0 11.5 12.0 12.5
E;(eV)
FIG. 2 9 . R e s o n a n c e s p e c t r a in H 2 , for AJ = 0 ( f r o m J o y e z e t a l . , 1973).

I A E A - S M R - 1 2 / 2 6 , 27 599
:
(1) COMPLETE SPATIAL INVERSION
(REFLECTION
, SYMMETRY)
( 3 ) E X C H A N G E OF PROTON SPINS'.
\* 4 f
nuCl.Spin.' 1
( S Y M . S P I N STATE I
( 4 ) COMPLETE E X C H A N G E OF 2 PROTONS ' • ( + 1 ) ( - 1 ) ( + 1 ) M ) M ) = - 1
FIG.30. T h e s u c c e s s i v e o p e r a t i o n s (i) c o m p l e t e s p a t i a l i n v e r s i o n , (ii) i n v e r s i o n in e l e c t r o n s p a c e o n l y ,

a n d ( i i i ) proton spin e x c h a n g e , give e x c h a n g e of t h e p r o t o n s .
F i g u r e 29 shows r e s o n a n c e s p e c t r a in H 2 f o r the exit c h a n n e l s

(Av = 4, A J = 0) and ( A v = 6 , A J = 0). Both s e r i e s a and с a p p e a r in t h i s
c a s e . On the o t h e r hand, the s p e c t r a f o r which A J = 2 (in f a c t J; = 1 -> Jf =3),
a s shown in F i g . 30 a r e quite d i f f e r e n t . T h e r e a r e s e v e r a l u n u s u a l f e a t u r e s
in t h e s e s p e c t r a which we s h a l l e x p l a i n .
B e f o r e doing t h i s we have to c o n s i d e r the r e q u i r e m e n t s of n u c l e a r spin
s t a t i s t i c s . C o n s i d e r t h o s e t a r g e t m o l e c u l e s which have J ; = 1 (67% a r e like
t h i s , 14% have = 0, 11% have J; = 2, 8% have J, = 3, and a m u c h s m a l l e r
p e r c e n t a g e have h i g h e r v a l u e s of J j ) . The r o t a t i o n a l wave f u n c t i o n f o r t h e s e
m o l e c u l e s i s Y™ and t h e i r e l e c t r o n i c s y m m e t r y i s 1 I * . Now the c o - o r d i n a t e s
of the two p r o t o n s can be e x c h a n g e d by f i r s t l y r e f l e c t i n g all t h e p a r t i c l e s at
the o r i g i n (i. e. i n v e r s i o n ) and then r e f l e c t i n g only the e l e c t r o n s at the o r i g i n .
The f i r s t i n v e r s i o n can be a c c o m p l i s h e d by f i r s t l y i n v e r t i n g the v i b r a t i o n a l
wave f u n c t i o n (pvib (which d o e s nothing to the c o m p l e t e wave f u n c t i o n Ф ), then
i n v e r t i n g the r o t a t i o n a l wave f u n c t i o n Yj^1' (which m u l t i p l i e s \ř by (-) J i ), and
t h e n i n v e r t i n g the e l e c t r o n i c wave f u n c t i o n <pe (this can be done by r o t a t i n g
it t h r o u g h 180° about an a x i s p e r p e n d i c u l a r to the i n t e r n u c l e a r a x i s , which
d o e s not i n f l u e n c e cpe s i n c e it d e p e n d s only on the c o - o r d i n a t e s of the
e l e c t r o n s r e l a t i v e to the n u c l e i , and then r e f l e c t i n g <pe t h r o u g h a p l a n e
600 ' READ
c o n t a i n i n g the i n t e r n u c l e a r a x i s and p e r p e n d i c u l a r to the f i r s t a x i s , which

r e s u l t s in m u l t i p l y i n g <p by +1 o r - 1 , depending on i t s r e f l e c t i o n s y m m e t r y ) .
The s e c o n d i n v e r s i o n , of t h e e l e c t r o n s only, m u l t i p l i e s i- by +1 if cpe h a s
g - s y m m e t r y , and by - 1 if it h a s u - s y m m e t r y . T h e s e a r g u m e n t s have b e e n
given by H e r z b e r g (1950). To s u m m a r i z e t h e m , we can s a y that the
x
nuclear co-ordinate exchange s y m m e t r y = ( - / ' X (4.4)
The m i d d l e t e r m c h a r a c t e r i z e s r e f l e c t i o n s y m m e t r y . T h e r e f o r e , H 2 m o l e -
c u l e s having J j = 1 and being in 1 Eg e l e c t r o n s t a t e s a r e a n t i s y m m e t r i c with
r e s p e c t to e x c h a n g e of the p r o t o n c o - o r d i n a t e s . Now exchange of the p r o t o n
c o - o r d i n a t e s and exchange of p r o t o n s p i n s a m o u n t s to t o t a l e x c h a n g e of the
two p r o t o n s , and t h i s m u s t give the r e s u l t - 1 s i n c e the p r o t o n s a r e f e r m i o n s .
T h e r e f o r e the spin e x c h a n g e m u s t be s y m m e t r i c , which m e a n s that the two
p r o t o n s a r e in a t r i p l e t spin s t a t e , with t h e i r s p i n s aligned p a r a l l e l to e a c h
other.
It f o l l o w s t h a t t h o s e H 2 m o l e c u l e s in which t h e p r o t o n s have p a r a l l e l
spin ( o r t h o h y d r o g e n ) m u s t have odd v a l u e s of J j , and p a r a h y d r o g e n m o l e -
c u l e s m u s t have e v e n v a l u e s of An i m m e d i a t e c o n s e q u e n c e of t h i s i s
t h a t A J = J f - Jj can only be e v e n , f o r both t y p e s of m o l e c u l e .
B e f o r e we can u n d e r s t a n d t h e r o t a t i o n a l s t r u c t u r e of r e s o n a n t t r a n s i t i o n s
we h a v e to d e r i v e a f u r t h e r s e l e c t i o n r u l e which s e e m s to apply to e l e c t r o n
c o l l i s i o n s only. C o n s i d e r the plane c o n t a i n i n g the i n t e r n u c l e a r a x i s and the
d i r e c t i o n of the i n c i d e n t e l e c t r o n . The m o l e c u l a r wave f u n c t i o n h a s p o s i t i v e
r e f l e c t i o n s y m m e t r y in t h i s plane (since it i s a £ + s t a t e ) , o r in any o t h e r
p l a n e t h r o u g h the i n t e r n u c l e a r axis. The wave f u n c t i o n f o r the incident
e l e c t r o n p l a n e wave i s exp (ik • r ) , which a l s o h a s p o s i t i v e r e f l e c t i o n s y m m e t r y
in t h i s p l a n e , but not in o t h e r p l a n e s which do not contain the d i r e c t i o n k.
T h e r e f o r e in the s p e c i f i e d p l a n e the c o m p l e t e i n i t i a l wave f u n c t i o n f o r t h e
s y s t e m of t a r g e t p l u s e l e c t r o n h a s p o s i t i v e r e f l e c t i o n s y m m e t r y . But the
r e s o n a n t s t a t e m u s t a l s o have t h i s s y m m e t r y in t h i s p l a n e , s i n c e t h e i n t e r -
action cannot change the s y m m e t r y . Since the r e s o n a n t s t a t e t h e r e f o r e h a s
p o s i t i v e r e f l e c t i o n s y m m e t r y in the s p e c i f i e d p l a n e , it m u s t also h a v e t h i s
s a m e s y m m e t r y f o r any p l a n e p a s s i n g t h r o u g h i t s i n t e r n u c l e a r a x i s .
T h i s s a m e a r g u m e n t a p p l i e s to any d i a t o m i c m o l e c u l a r r e s o n a n c e .
It m e a n s that in the t r a n s i t i o n f r o m the t a r g e t m o l e c u l e to the r e s o n a n t
compound s t a t e the r e f l e c t i o n s y m m e t r y cannot change, and one h a s the
selection rule for reflection s y m m e t r i e s
+ -<—>-, + -1/-* - (4.5)
S i m i l a r r e a s o n i n g h a s b e e n u s e d by C a r t w r i g h t et al. (1971) in connection

with s e l e c t i o n r u l e s in i n e l a s t i c E <—• E" t r a n s i t i o n s , but we will d e a l with
t h i s t o p i c l a t e r . The r e l e v a n c e to e - H 2 r e s o n a n c e s i s t h a t all the r e s o n a n t
s t a t e s m u s t have p o s i t i v e r e f l e c t i o n s y m m e t r y b e c a u s e t h e t a r g e t m o l e c u l e s
have this s y m m e t r y .
Now we s h a l l b r i n g t o g e t h e r t h e s e i d e a s on n u c l e a r spin s t a t i s t i c s and
on r e f l e c t i o n s y m m e t r i e s . The r e s t r i c t i o n on the r e f l e c t i o n s y m m e t r y l e a d s
i m m e d i a t e l y to r e s t r i c t i o n s on the allowed v a l u e s of J r , b e c a u s e of the
I A E A - S M R - 1 2 / 2 6 , 27 601
c o n c u r r e n t r e q u i r e m e n t s of n u c l e a r spin s t a t i s t i c s . F o r e x a m p l e if the
t a r g e t m o l e c u l e h a s an odd value of J ; , and the r e s o n a n t s t a t e h a s sym-
m e t r y , then it m u s t a l s o have an odd value of J r , s i n c e it h a s the s a m e
reflection s y m m e t r y . That is
Jr - J ; = e v e n f o r £g £g, or £ u «—• £ u
J r - J j = o d d f o r £ g — Eu (4.6)
T h i s i s a l s o t r u e f o r p a r a h y d r o g e n , and m o r e g e n e r a l l y f o r all h o m o n u c l e a r
diatomic molecules.
F i g u r e 31 shows a s e t of s p e c t r a which can only be u n d e r s t o o d with the
help of s e l e c t i o n r u l e (4.6). By p o s t u l a t i n g v a r i o u s s y m m e t r i e s of the
r e s o n a n t s t a t e one i s p o s t u l a t i n g the p o s s i b l e v a l u e s of and S 2 and the
p o s s i b l e v a l u e s of J r which could be o b s e r v e d . F i g u r e s 32, 33, and 34
show the c o n s e q u e n c e s of v a r i o u s p o s t u l a t e s . It can be s e e n that the only
s y m m e t r y which i s c o n s i s t e n t with the o b s e r v a t i o n s i s
1 1 1 1 1 1 1 ! 1 . 1
J i =J r " J ,
Jr = 1 3 j r - 3 - J , =1
I I
' * •-.
"Л"
J =3 J|=1—J,=5
1
Jr= 1 3 Jj = 1 — J t = 3
J r -- 0 2 J ( = 2 — ' J, = 0
Jr=3 5 J *3-~Jf=5 i l .
... .. i 1
i1 i! i1 i! i1 11 1 1 1 i1 i
1— i
11.0 11.5 11.0 11.5
Ej (eV)
FIG.31. Resonant e x c i t a t i o n f u n c t i o n s in H 2 . T h e s c a t t e r i n g a n g l e is 25°, a n d A v = 1 ( f r o m J o y e z e t a l . , 1 9 7 3 ) .

READ
RESONANT STATE
Ji Л -FORBIDDEN
1 o- FOR A n-STATE
?1G. 33. C o n s e q u e n c e s of t h e p o s t u l a t e for s t a t e Л
RESONANT STATE *£„••
Jr(—Nr )
- 0
FIG. 34. C o n s e q u e n c e s of t h e p o s t u l a t e for s t a t e I

IAEA-SMR-12/26, 27 603
T A B L E II. VALUES O F J r WHICH SHOULD BE OBSERVED WHEN

J, = J f
Symmetry J; = Possible J r
2
£+ 0 0, 2
g
1 1,3
2 0,2,4
3 1,3,5
0 2
4 •
1 1,2,3
2 1 , 2 , 3, 4
3 1,2,3,4,5
0 2
4
1 2,3
2 2,3,4
3 2, 3, 4 , 5
1 0,2
2 1,3
3 2,4
4 0 1
1 ' 1,2
2 1, 2 , 3
3 2,3,4
The incident e n e r g y at which a l e v e l J r should be o b s e r v e d is
E, = E r + Br J r (J r + 1) - B, J; (Jj + 1 ) (4. 7)
w h e r e E r i s the p u r e l y v i b r o n i c p a r t of the r e s o n a n c e e n e r g y . T h i s f o r m u l a
f i t s the d a t a of T a b l e II quite n i c e l y , and g i v e s B r = 4.3 m e V , which m e a n s
t h a t the e q u i l i b r i u m i n t e r n u c l e a r s e p a r a t i o n of the r e s o n a n t s t a t e i s 0.98 Â.
T h e s e v a l u e s a r e c o n s i s t e n t with t h o s e of p o s s i b l e p a r e n t s t a t e s of t h e
resonance.
6 0 4 ' READ
.CALCULATED
OBSERVED
О"-"
APPARATUS
\ FUNCTION
// о°
/
РОСС*?
асрин! - ^ -cГ t1 r o
0 24 026 0.28 0.30 0.32 0.34
ENERGY LOSS (eV)
FIG.35. C o m p a r i s o n b e t w e e n e x p e r i m e n t a n d t h e o r y for e n e r g y loss d i s t r i b u t i o n in N z ( f r o m C o m e r and

Harrison, 1973).
Although the r o t a t i o n a l s t r u c t u r e of H 2 h a s b e e n r e s o l v e d , it m a y be
a y e a r o r two yet b e f o r e it will be r e s o l v e d f o r o t h e r m o l e c u l e s . N e v e r -
t h e l e s s it h a s s t i l l been p o s s i b l e to m a k e d e d u c t i o n s f r o m u n r e s o l v e d s p e c t r a .
F o r e x a m p l e , C o m e r and H a r r i s o n (1973) have r e c e n t l y shown that
the o b s e r v e d r e s o n a n c e s in N 2 at about 2.3 eV a r e m e a s u r a b l y b r o a d e n e d
b y t h e i r r o t a t i o n a l s t r u c t u r e . The r e s o n a n c e s y m m e t r y i s Z n g , t h e r e f o r e
I J f - J j I h a s a m a x i m u m value of 4. T h e r e a r e m a n y d i f f e r e n t t r a n s i t i o n s
J. -» J f (the m o s t p o p u l a t e d l e v e l i s that h a v i n g J\ = 8), and t h e y a r e too n e a r
t o g e t h e r in e n e r g y to be r e s o l v e d , but n e v e r t h e l e s s the r e s o n a n t p e a k s a r e
b r o a d e n e d by the p r e s e n c e of t r a n s i t i o n s having | A J | = 2 and 4. The o b s e r v e d
b r o a d e n i n g e s t a b l i s h e s t h e 2 n g s y m m e t r y , so t h i s m e t h o d i s an a l t e r n a t i v e to
m e a s u r i n g a n g u l a r d i s t r i b u t i o n s . F i g u r e 35 shows the a g r e e m e n t b e t w e e n
the o b s e r v e d and c a l c u l a t e d p e a k s h a p e s .
I A E A - S M R - 1 2 / 2 6 , 27 605
5. DETERMINATION O F G E N E R A L I Z E D OSCILLATOR STRENGTHS

FOR TRANSITIONS IN N E U T R A L M O L E C U L E S
Much of the w o r k on t h i s s u b j e c t h a s b e e n done by L a s s e t t r e and h i s

c o l l e a g u e s . Some r e f e r e n c e s to the work can be found in h i s r e v i e w
( L a s s e t t r e , 1969). The B o r n a p p r o x i m a t i o n i s u s e d e x t e n s i v e l y in i n t e r -
p r e t i n g the r e s u l t s , and an e x c e l l e n t r e v i e w of t h i s a p p r o x i m a t i o n h a s
b e e n given by Inokuti (1971).
C o n s i d e r an i n e l a s t i c c o l l i s i o n in which the i n c i d e n t e l e c t r o n h a s
m o m e n t u m h k x and the s c a t t e r e d e l e c t r o n h a s m o m e n t u m ftk2. The e n e r g y
l o s t by the e l e c t r o n and gained by the m o l e c u l e i s t h e r e f o r e
w = k 2 k
Ž 
(we s h a l l i g n o r e c e n t r e - o f - m a s s e f f e c t s , and t r e a t the m o l e c u l e a s being

m u c h h e a v i e r than the e l e c t r o n ) . It i s u s e f u l to d e f i n e the m o m e n t u m
transfer
ïiK = h (k a k2) (5.2)
A c c o r d i n g to the B o r n a p p r o x i m a t i o n (which i s e x p e c t e d to be valid

at high i n c i d e n t e n e r g i e s ) the d i f f e r e n t i a l c r o s s - s e c t i o n d a / d f 2 f o r an i n e l a s t i c
s c a t t e r i n g p r o c e s s i s a f u n c t i o n of k 1 ; k 2 , K, and W only. In f a c t t h i s
approximation gives
d n kj W K2 Sen
w h e r e f , the " g e n e r a l i z e d o s c i l l a t o r s t r e n g t h " i s a f u n c t i o n of К and W,

but not of k x and k 2 .
We s h a l l now l e a v e the u s u a l w a y s of t r e a t i n g f g e n (e. g. L a s s e t t r e , 1969,
Inokuti,1971), which a r e b a s e d e s s e n t i a l l y on a t o m i c s c a t t e r i n g p r o c e s s e s ,
and give i n s t e a d an e s s e n t i a l l y m o l e c u l a r t r e a t m e n t of t h e g e n e r a l i z e d
oscillator strength.
If no a s s u m p t i o n s a r e m a d e about the v a r i a t i o n of e l e c t r o n i c t r a n s i t i o n
m o m e n t s with i n t e r n u c l e a r d i s t a n c e , and it i s a s s u m e d that r o t a t i o n a l
s t r u c t u r e i s not r e s o l v e d , t h e n it can be shown t h a t f o r the t r a n s i t i o n
n'v1 nv (where n and v r e p r e s e n t e l e c t r o n i c and v i b r a t i o n a l q u a n t u m
606 ' READ
n u m b e r s r e s p e c t i v e l y ) t h e g e n e r a l i z e d o s c i l l a t o r s t r e n g t h c a n be e x p a n d e d a s
00
(5 4)
fgen(nv' -nv) 2, -
{ =0
where
+ й
= ^ |Nď,m)|2 (5.5)
m = -I
and
N ( í , m ) = / vib(v |Ř) <pel ( n | ? j , R) d?j dït (5.6)

->
A l l q u a n t i t i e s a r e in a t o m i c u n i t s . R r e p r e s e n t s the v i b r a t i o n a l c o - o r d i n a t e s ,
r . t h e e l e c t r o n i c c o - o r d i n a t e s . T h i s e x p a n s i o n of f w a s given b y R e a d
and W h i t e r o d (1963). An a d v a n t a g e of it i s t h a t e a c h N(i>,m) h a s an i n t e g r a n d
of d e f i n i t e s y m m e t r y , and one can u s e g r o u p - t h e o r e t i c a l m e t h o d s to e s t a b l i s h
which of t h e m v a n i s h . If it c a n be a s s u m e d t h a t t h e e l e c t r o n i c wave f u n c t i o n s
v a r y s l o w l y with t h e v i b r a t i o n a l c o - o r d i n a t e s R t h e n one could s e p a r a t e N ( ( , m )
into an e l e c t r o n i c p a r t and a v i b r a t i o n a l p a r t , and t h i s l a t t e r p a r t g i v e s t h e
F r a n c k - C o n d o n o v e r l a p f a c t o r of c o u r s e .
T h e e x p e r i m e n t s have m o s t l y b e e n c a r r i e d out in s u c h a w a y t h a t the
m o m e n t u m К i s a s s m a l l a s p o s s i b l e . T h i s i s a c h i e v e d by u s i n g high i n c i d e n t
e n e r g i e s E j (Ž. a f e w 100 eV) and s m a l l s c a t t e r i n g a n g l e s в a few d e g r e e s ) .
In f a c t
K2~8E {sin2f
I 2 \ 4 E
where
- W
(5.7)
T h e l e a d i n g t e r m s in f g e n , when К i s s m a l l , can be e s t a b l i s h e d e a s i l y
f r o m t h e f o r m u l a s given a b o v e . F o r s m a l l a r g u m e n t s x the s p h e r i c a l B e s s e l
f u n c t i o n s j c (x) c a n b e e x p a n d e d
j0(x) = 1 - +
. / » Л Л.
J
1(X) =
3 - 3Ö+---
j2(x)=T5 + ... (5.8)

IAEA- S M R - 1 2 / 2 6 , 2 7 607
Now the f i r s t t e r m in j 0 would m a k e N ( 0 , 0 ) p r o p o r t i o n a l to K° and h e n ^ e f g e n

p r o p o r t i o n a l to КГ2 . H o w e v e r , one can s e e i m m e d i a t e l y t h a t t h i s d o e s not
happen b e c a u s e the v i b r o n i c wave f u n c t i o n s a r e o r t h o g o n a l and t h i s l e a d i n g
t e r m in N(0, 0) v a n i s h e s .
The next h i g h e s t p o w e r of К c o m e s f r o m t h e f i r s t t e r m in t h e e x p a n s i o n
of j j f K r j ) ; N ( l , m ) i s p r o p o r t i o n a l to K, and t h e r e f o r e f i s p r o p o r t i o n a l to
K°. T h i s f i r s t , c o n s t a n t , t e r m in the e x p a n s i o n of the g e n e r a l i z e d o s c i l l a t o r
s t r e n g t h i s a c t u a l l y the o p t i c a l o s c i l l a t o r s t r e n g t h f o p t which g o v e r n s photon
a b s o r p t i o n and e m i s s i o n c r o s s - s e c t i o n s (for e l e c t r i c dipole t r a n s i t i o n s ) ,
f t i s n o n - z e r o only if the s e l e c t i o n r u l e s f o r o p t i c a l t r a n s i t i o n s a r e f u l -
f i l l e d (in e f f e c t the s a m e s e l e c t i o n r u l e s d e t e r m i n e w h e t h e r o r not the m a t r i x
elements N ( l , m ) are non-zero).
The n e x t h i g h e s t p o w e r of К (namely K 2 ) c o m e s f r o m M 0 (the second
t e r m in the e x p a n s i o n of jQ), f r o m Mj (a c r o s s p r o d u c t involving t h e f i r s t
and s e c o n d t e r m s in the e x p a n s i o n of j j ) , and f r o m M 2 . Again t h e r e m a y
be s y m m e t r y r e a s o n s c a u s i n g one o r m o r e of t h e s e c o n t r i b u t i o n s to v a n i s h .
С 5
20000
18000
16000
А'П
14000
E П
R 12000
к 10000
ai 8000
6000
4000
2000
Я T 1
l.o
1 1 г
9.0
i I I I I I i I I
10.0 11.0
wi
1
12.0
г
ENERGY LOSS(eV)
FIG. 36. E n e r g y loss s p e c t r u m of C O as o b t a i n e d by L a s s e t t r e a n d S k e r b e l e ( 1 9 7 1 ) .

6 0 8 ' READ
о 300 eV
л 400 eV
.U
• 500 eV
' V .
_j i '
0.10 0.20 0.30 0.40
[ЛР)2
FIG.37. Oscillator strengths obtained f r o m measured d i f f e r e n t i a l cross-sections (from Lassettre and Skerbele, 1971).
/
/
/
/
-/
/
0t i ' I I 1 I i I i i i
0.1 0.2
tAP)2 '
FIG. 3 8 . M e a s u r e d v a l u e s of f „ e n for o p t i c a l l y f o r b i d d e n t r a n s i t i o n ( L a s s e t t r e , p r i v a t e c o m m u n i c a t i o n ) .
IAEA-SMR-12/26, 27 609
In g e n e r a l we m a y w r i t e t h e r e f o r e
f gen = f opt + ) a n*K 2n v(5.9)'

n—1
The p u r p o s e of m o s t of t h e e x p e r i m e n t s h a s b e e n (i) to d e t e r m i n e f o p t
f o r allowed t r a n s i t i o n s , o r (ii) to show that f^ e n t e n d s to z e r o a s К t e n d s to
z e r o f o r o p t i c a l l y f o r b i d d e n t r a n s i t i o n s , o r (lii) to t e s t the v a l i d i t y of the
Born approximation.
F i g u r e 36 s h o w s an e n e r g y l o s s s p e c t r u m of CO by L a s s e t t r e and
S k e r b e l e (1971). The g e n e r a l i z e d o s c i l l a t o r s t r e n g t h s which t h e y w e r e
able to d e r i v e f r o m m e a s u r i n g d i f f e r e n t i a l c r o s s - s e c t i o n s a r e shown in
F i g . 37. As i s u s u a l , t h e y have plotted f g e n a g a i n s t K 2 , and one can s e e
that E q . (5.9) s e e m s to be followed. Note that f g e n i s a f u n c t i o n of K, but
i s i n d e p e n d e n t of the incident e n e r g y E i ( which s e e m s to show t h a t the
B o r n a p p r o x i m a t i o n i s valid f o r t h e s e r e s u l t s .
M e a s u r e d v a l u e s of f g e n f o r an o p t i c a l l y f o r b i d d e n t r a n s i t i o n a r e shown
in F i g . 3 8. A s e x p e c t e d f g e n t e n d s to z e r o a s К t e n d s to z e r o . F i g u r e 39
shows a n o t h e r f o r b i d d e n t r a n s i t i o n , but t h i s t i m e t h e r e i s a d e p e n d e n c e on
t h e i n c i d e n t e n e r g y , which s e e m s to i n d i c a t e t h a t the B o r n a p p r o x i m a t i o n i s
not v e r y good f o r t h i s t r a n s i t i o n . In fact L a s s e t t r e and h i s c o l l e a g u e s have
n o t i c e d o t h e r 1 E + <- •fc* t r a n s i t i o n s f o r which the B o r n a p p r o x i m a t i o n i s not
v a l i d . T h e r e i s s o m e r e a s o n to b e l i e v e f r o m e l e c t r o n - a t o m s t u d i e s t h a t
the B o r n a p p r o x i m a t i o n i s not a l w a y s r e l i a b l e at t h e s e e n e r g i e s .
0.012 r
/
"/
/
Ol I 1 I I I I 1 I 1 i i i i ' i
0.1 0.2 0.3
2
(ДР!
FIG.39. Energy-dependent f „ e n curve for optically forbidden transition (Lassettre, private communication).
610 ' READ
In the c a s e of p o l y a t o m i c m o l e c u l e s the p h e n o m e n o n of " b o r r o w e d

o s c i l l a t o r s t r e n g t h " o c c u r s in e l e c t r o n i m p a c t t r a n s i t i o n s , a s it d o e s f o r
photon t r a n s i t i o n s . C o n s i d e r two e l e c t r o n i c s t a t e s which have s y m m e t r i e s
such t h a t e l e c t r i c - d i p o l e o p t i c a l t r a n s i t i o n s a r e f o r b i d d e n b e t w e e n t h e m .
If q u a n t a of v i b r a t i o n a r e e x c i t e d in one of t h e s e s t a t e s , and if the v i b r a t i o n a l
m o d e h a s s o m e a s y m m e t r y in it, then t h i s v i b r a t i o n a l m o t i o n m a y m i x in
o t h e r e l e c t r o n i c s y m m e t r i e s . T h i s a d m i x t u r e m a y then c a u s e an allowed
t r a n s i t i o n , and in t h i s way the t r a n s i t i o n " b o r r o w s " o s c i l l a t o r s t r e n g t h f r o m
the a d m i x e d s t a t e s .
In p r a c t i c e it s e e m s to be t r u e (although in p r i n c i p l e it i s p e r h a p s not
a l w a y s t r u e ) that t h e r e i s a l w a y s s o m e v i b r a t i o n a l m o d e with a s y m m e t r y
which can c a u s e such b o r r o w i n g , so that if v i b r a t i o n a l s t r u c t u r e i s not
r e s o l v e d it would a p p e a r a s though a l l e l e c t r o n i c t r a n s i t i o n s in p o l y a t o m i c
m o l e c u l e s h a v e s o m e allowed c h a r a c t e r . In t h i s c a s e fg en would not go to
z e r o f o r s m a l l K, but t h i s h a s not yet b e e n studied t h o r o u g h l y .
B e f o r e l e a v i n g the q u e s t i o n of i n e l a s t i c s c a t t e r i n g , it should be m e n t i o n e d
t h a t C a r t w r i g h t e t a l . (1971) have pointed out an u n u s u a l f e a t u r e of £ + E~
t r a n s i t i o n s , such a s the b-'Eg x 1 E g t r a n s i t i o n in 0 2 . It h a s b e e n noticed
f r o m t h e work of C a r t w r i g h t e t al. and L a s s e t t r e et al. , t h a t t h e s e t r a n s i -
t i o n s have v e r y s m a l l d i f f e r e n t i a l c r o s s - s e c t i o n s , p a r t i c u l a r l y n e a r 0°,
w h e r e t h e y go r a p i d l y to z e r o .
T h i s can be explained by an e x t e n s i o n of the a r g u m e n t s on r e f l e c t i o n
s y m m e t r y u s e d in s e c t i o n 4, T h e r e it w a s shown t h a t the r e f l e c t i o n s y m m e t r y
i s c o n s e r v e d in the p l a n e containing the m o l e c u l a r a x i s and the incident b e a m
d i r e c t i o n . Now if the i n e l a s t i c e l e c t r o n i s s c a t t e r e d t h r o u g h 0° o r 180" t h e n
the outgoing p l a n e wave h a s p o s i t i v e r e f l e c t i o n s y m m e t r y in t h i s p l a n e and
t h e r e f o r e the f i n a l m o l e c u l e m u s t have the s a m e r e f l e c t i o n s y m m e t r y a s the
i n i t i a l m o l e c u l e . The s e l e c t i o n r u l e (4.5) t h e r e f o r e a p p l i e s to t h e s e i n e l a s t i c
scattering events.
T h i s m e a n s that it i s not p o s s i b l e to e x c i t e a E~ s t a t e if the t a r g e t
m o l e c u l e was in a £ + s t a t e , and if the angle of s c a t t e r i n g i s 0° o r 180°.
F o r s t a t e s of h i g h e r A, only t h e f o r m s of p o s i t i v e r e f l e c t i o n s y m m e t r y
would be e x c i t e d . It is c l e a r then that the d i f f e r e n t i a l c r o s s - s e c t i o n s f o r
E t r a n s i t i o n s m u s t be z e r o in the f o r w a r d and b a c k w a r d d i r e c t i o n s .
One m i g h t a r g u e that the c r o s s - s e c t i o n would in any c a s e be s m a l l in the
f o r w a r d d i r e c t i o n b e c a u s e such t r a n s i t i o n s a r e a l w a y s o p t i c a l l y f o r b i d d e n
and t h e r e f o r e the g e n e r a l i z e d o s c i l l a t o r s t r e n g t h would be s m a l l . H o w e v e r ,
it i s c l e a r t h a t the r e s t r i c t i o n i m p o s e d by the n e c e s s i t y to c o n s e r v e r e f l e c -
tion s y m m e t r y i s m o r e p o w e r f u l , and i s valid at all i n c i d e n t e n e r g i e s .
T h i s f e a t u r e of the b e h a v i o u r of E~ •E + t r a n s i t i o n s w a s f i r s t e x p l a i n e d
by C a r t w r i g h t et al. (1971), u s i n g s o m e w h a t d i f f e r e n t r e a s o n i n g .
When i n e l a s t i c e l e c t r o n s a r e s c a t t e r e d in the f o r w a r d d i r e c t i o n , the
e x c i t e d m o l e c u l e m a y be l e f t with a d i s t r i b u t i o n of s u b - s t a t e s which i s not
n o r m a l . F o r e x a m p l e , only p o s i t i v e r e f l e c t i o n s y m m e t r y would be found
(if the t a r g e t h a s t h i s s y m m e t r y ) . In the c a s e of a t o m s the e x c i t e d s t a t e s
m a y be l e f t with a d i s t r i b u t i o n of m a g n e t i c q u a n t u m n u m b e r s w h i c h i s not
u n i f o r m , and t h e r e f o r e the d e - e x c i t a t i o n p h o t o n s a r e p o l a r i z e d in g e n e r a l .
T h i s h a s b e e n shown r e c e n t l y by King, A d a m s and R e a d (1972). T h e s a m e
i s no doubt t r u e of m o l e c u l e s . It m a y t h e r e f o r e be i n t e r e s t i n g in the f u t u r e
to m e a s u r e the w a v e l e n g t h s and p o l a r i z a t i o n s of p h o t o n s which a r e d e t e c t e d
in c o i n c i d e n c e with e l e c t r o n s s c a t t e r e d in the f o r w a r d d i r e c t i o n .
I A E A - S M R - 1 2 / 2 6 , 27 611
6. DETERMINATION O F L I F E T I M E S O F E X C I T E D S T A T E S O F
N E U T R A L M O L E C U L E S BY E L E C T R O N SCATTERING METHODS
T h e r e a r e s e v e r a l d i f f e r e n t ways of m e a s u r i n g the d e c a y l i f e t i m e s of
e x c i t e d s t a t e s of m o l e c u l e s . The m o s t u s u a l m e t h o d i s to e x c i t e the m o l e - '
c u l e s in a g a s c e l l by a p u l s e of i n c i d e n t e l e c t r o n s o r p h o t o n s , and to m o n i t o r
the d e - e x c i t a t i o n p h o t o n s a s a f u n c t i o n of t i m e a f t e r the c e s s a t i o n of the
exciting pulse. Unfortunately this method usually suffers f r o m "cascading",
a s i l l u s t r a t e d on F i g . 40. A n o t h e r m e t h o d i s to u s e the Hanle e f f e c t . In t h i s
a p a r t i c u l a r r o v i b r o n i c l e v e l i s e x c i t e d by light f r o m an a t o m i c line which
h a s the s a m e e n e r g y (this c o i n c i d e n c e in e n e r g i e s i s r a r e , but not unknown),
and then the e x c i t e d m o l e c u l a r l e v e l i s r o t a t e d in s p a c e by a u n i f o r m m a g n e t i c
f i e l d , at a r a t e which d e p e n d s on the g y r o m a g n e t i c r a t i o of the s t a t e (and
t h e r e f o r e t h i s m u s t be known). W h i l s t r o t a t i n g t h e s t a t e d e c a y s by e m i t t i n g
p h o t o n s , and the m e a s u r e d photon y i e l d s can be u s e d to give the l i f e t i m e of
the s t a t e . O t h e r m e t h o d s of m e a s u r i n g l i f e t i m e s have b e e n applied to a t o m s ,
but not o f t e n to m o l e c u l e s . A r e c e n t r e v i e w h a s b e e n given by C o r n e y (1970).
L e t u s d i s c u s s a r e c e n t l y d e v e l o p e d m e t h o d which a l l o w s l i f e t i m e s to
be m e a s u r e d quite a c c u r a t e l y , and which s e e m s to be f r e e of m o s t of the
s y s t e m a t i c e r r o r s which e x i s t in m a n y o t h e r m e t h o d s . T h i s i s the e l e c t r o n -
photon c o i n c i d e n c e m e t h o d : a d e s c r i p t i o n of it can be found in Imhof and
R e a d (1971a). The b a s i s of the m e t h o d i s shown s c h e m a t i c a l l y in F i g . 41.
A t y p i c a l r e s u l t i s shown in F i g . 15. Note the c o n s t a n t b a c k g r o u n d of
u n r e l a t e d e v e n t s . The r i s i n g p a r t of the c u r v e i s not s h a r p b e c a u s e t h e r e
i s a t i m e s p r e a d of a few n s in t h e m e a s u r i n g p r o c e s s : in e f f e c t an " a p p a r a t u s
f u n c t i o n " of f i n i t e width h a s to be convoluted with the e x p o n e n t i a l l y d e c r e a s i n g
d e c a y c u r v e . If the a p p a r a t u s f u n c t i o n h a s a G a u s s i a n s h a p e with a s t a n d a r d
d e v i a t i o n then t h i s convoluted c u r v e h a s t h e f o r m
f(t) = A + В {l + erf ( h t - exp -7 ) (6.1)
w h e r e т i s the l i f e t i m e and h = (ст -/2)" : The f u l l line in the plot is a n o n -

l i n e a r l e a s t - s q u a r e s fit of t h i s f u n c t i o n to the e x p e r i m e n t a l r e s u l t s .
FIG.40. Scheme illustrating decay l i f e t i m e measurements of excited states. Left-hand: If state a were
the only one to be excited, the photons of X. 1 would arrive with exponentially decreasing time probability
as shown in right-hand graph. If higher states are excited, cascading can occur from them to level a and
the decay curve for \ i would be non-exponential.
612 ' READ
FIG. 41. Schematic block diagram for electron-photon coincidence method.
T A B L E III. NITROGEN с 3Пи L I F E T I M E ( f r o m Imhof and R e a d , 1971b)
(1) M e a s u r e d by the e l e c t r o n - p h o t o n c o i n c i d e n c e m e t h o d
V r(ns) Number of independent

determinations
0 35.6 ± 0 . 5 7
1 34.9 i 1 . 8 2
2 34. 5 ± 2. 3 2
(2) P r e v i o u s m e a s u r e m e n t s
T (ns) Technique Authors
46.3 ± 1 Beam foil L.L. Nichols, N.E, Wilson 1968
39.7 ± 1 . 6 Beam foil J. Desesquelles et al. 1968
48 ±8 Phase-shift e - b e a m J. Hesser 1968
37 ±3 Phase-shift e - b e a m H. Anton 1966
49 ±5 Pulsed R.F. discharge M. Jeunehomme 1966
29 ±7 Intensity in a D. C. arc E. Brusyanova et al. 1965
35. 5 ± 2 Pulsed D. C. discharge K. Wagner 1964
27 ±5 Phase-shift e - b e a m E. Fink, К. Welge 1964
44.5 ± 6 Pulsed e - b e a m W,R. Bennett, F . W . Dalby 1959

I A E A - S M R - 1 2 / 2 6 , 27 613
T(ns)
CO: A - X TRANSITION
12
О PRESENT WORK
X M U M M A , STONE A N D ZIPF (1971)
И WELLS A N D ISLER (1970)
A H E S S E R (1968)
v 9
\
\
4 -
ч
1 ;
6 V
FIG.42. Dependence of lifetime of A ' t state of CO on vibrational quantum number (from Imhof and Read, 1971c).
The r e a s o n f o r u s i n g a m e t h o d a s t e c h n i c a l l y d i f f i c u l t a s t h i s , i s that
it a v o i d s m o s t of the e r r o r s p r e s e n t in m a n y o t h e r m e t h o d s . That t h e s e
e r r o r s e x i s t i s a p p a r e n t f r o m the f a c t t h a t it i s p o s s i b l e f o r a few d i f f e r e n t
g r o u p s to m e a s u r e the s a m e l i f e t i m e and to get v a l u e s which d i f f e r by an
o r d e r of m a g n i t u d e j The m a i n s o u r c e s of s y s t e m a t i c e r r o r s a r e (i) c a s -
c a d i n g , (ii) photon t r a p p i n g , (iii) c o l l i s i o n a l d e - e x c i t a t i o n , (iv) r e c i p r o c a l
t r a n s f e r , (v) f i n i t e t i m e r e s o l u t i o n , (vi) n o n - l i n e a r i t i e s in t i m e - t o - p u l s e
height c o n v e r t e r s and m u l t i - c h a n n e l a n a l y s e r s , and (vii) p i l e - u p e f f e c t s .
In g e n e r a l a l l t h e s e a r e a b s e n t , o r can be m a d e n e g l i g i b l y i m p o r t a n t , in
the e l e c t r o n - p h o t o n c o i n c i d e n c e m e t h o d , e x c e p t e r r o r (v).
T a b l e III shows s o m e l i f e t i m e s m e a s u r e d in N 2 . Note that the l i f e t i m e
of the с 3 П и s t a t e d e p e n d s on the v i b r a t i o n a l q u a n t u m n u m b e r . F i g u r e 42
s h o w s a m o r e s t r i k i n g e x a m p l e of t h i s p h e n o m e n o n . It was noted in s e c t i o n 5
t h a t the m a t r i x e l e m e n t N(jP,m) (for photon e m i s s i o n one h a s i = 1) c a n be
614 ' READ
FIG.43. Electron energy loss spectrum for H 2 (from Imhof and Read, 1971b).
f a c t o r i z e d into an e l e c t r o n i c p a r t and a F r a n c k - C o n d o n f a c t o r , if the e l e c -

t r o n i c wave f u n c t i o n s a r e n e a r l y independent of the i n t e r n u c l e a r d i s t a n c e R
(over the r a n g e of R c o v e r e d b y the v i b r a t i o n a l wave f u n c t i o n s ) . If t h i s
f a c t o r i z a t i o n i s c a r r i e d out one f i n d s that the l i f e t i m e of a v i b r o n i c s t a t e
should be i n d e p e n d e n t of the v i b r a t i o n a l quantum n u m b e r (the c l o s u r e r u l e
f o r the v i b r a t i o n a l wave f u n c t i o n s of the f i n a l m o l e c u l e s p r o d u c e s t h i s r e s u l t ) ,
IAEA-SMR-12/26,27 6 1 5
T A B L E IV. HYDROGEN a 3 LIFETIME
V' T(ns) Technique Authors
0 11.0 i 0.42 1 electron-photon R.E. Imhof and F . H . Read, 1971b

г coincidence
1 10.6 i 0.6 J
35 ±8 pulsed electron R. Fowler and T. Holzberlein, 1966

beam
0 11.9
1 11.0
Calculation H.M. James and A.S. Coolidge, 1939
2 10.1
3 9.7
-
30 -
Q_
t ,
m
<
Ш
к 20 -
o_
I _
ь;
î
tn
Ш
>
ОС.
эu
о
cc
ш
ш
Z
3
z
0-20 20-40 40-60 60-80 80-100
FIG. 44. Histogram of x 2 _ probabilities.

616 ' READ
The o b s e r v a t i o n of l i f e t i m e s which depend on v ' can t h e r e f o r e be i n t e r -

p r e t e d as m e a n i n g that the e l e c t r o n i c wave f u n c t i o n s , and in p a r t i c u l a r the
e l e c t r o n i c t r a n s i t i o n m o m e n t , depend on R. O t h e r i n t e r p r e t a t i o n s a r e a l s o
p o s s i b l e , but t h e y would r e s u l t in n o n - e x p o n e n t i a l d e c a y c u r v e s , which a r e
not in fact o b s e r v e d .
F i g u r e 43 shows an e n e r g y l o s s s p e c t r u m of H 9 . The l i f e t i m e of the
3 +
a Eg s t a t e cannot be m e a s u r e d e a s i l y by the n o r m a l t e c h n i q u e s b e c a u s e it
d e c a y s to the r e p u l s i v e b 3 E * s t a t e and e m i t s a continuous band of w a v e l e n g t h s .
In the e l e c t r o n - p h o t o n c o i n c i d e n c e m e t h o d the whole band can be put in coin-
c i d e n c e with the i n e l a s t i c e l e c t r o n s . Table IV s h o w s s o m e r e s u l t s .
To t e s t t h e p o s s i b i l i t y of unknown s y s t e m a t i c e r r o r s in t h e s e l i f e t i m e
m e a s u r e m e n t s , a c h i - s q u a r e d a n a l y s i s h a s b e e n c a r r i e d out. F i g u r e 44
s h o w s a h i s t o g r a m of the " c h i - s q u a r e d p r o b a b i l i t y " v e r s u s c h i - s q u a r e d .
T h i s p r o b a b i l i t y should be u n i f o r m if the only e r r o r s a r e r a n d o m e r r o r s .
T h e t e c h n i q u e h a s now b e e n extended to c o v e r m o l e c u l a r ions (e. g. N 2 ,
CO + ) and r a d i c a l s ( e . g . NH, NH 2 ). In t h e s e c a s e s an i n e l a s t i c e l e c t r o n with
a d e f i n i t e e n e r g y d o e s not e x i s t to m a r k the t i m e at which t h e s e ions o r
r a d i c a l s a r e f o r m e d : i n s t e a d the i n e l a s t i c e l e c t r o n s have a r a n g e of e n e r g i e s .
N e v e r t h e l e s s it i s p o s s i b l e to s e l e c t a band of e l e c t r o n e n e r g i e s which can be
u s e d a s the t i m e m a r k e r s .
7. PREIONIZING STATES O F N E U T R A L ATOMS AND M O L E C U L E S
P r e i o n i z i n g (or autoionizing) s t a t e s of a t o m s o r m o l e c u l e s have an

e n e r g y above the ionization l i m i t and can d e - e x c i t e by e j e c t i n g an e l e c t r o n .
T h i s f o r m of d e - e x c i t a t i o n i s often r e f e r r e d to a s the A u g e r d e c a y p r o c e s s ,
and the e j e c t e d e l e c t r o n s as A u g e r e l e c t r o n s . T h e s e p r e i o n i z i n g s t a t e s
u s u a l l y have l i f e t i m e s which a r e much s h o r t e r than the l i f e t i m e s of s t a t e s
which can d e c a y by photon e m i s s i o n only.
P r e i o n i z i n g s t a t e s of s e v e r a l a t o m s and m o l e c u l e s have b e e n s e e n in
photon a b s o r p t i o n s p e c t r a , w h e r e they show up a s d i f f u s e l i n e s b e c a u s e of
t h e i r s h o r t l i f e t i m e . M o r e r e c e n t l y t h e s e s t a t e s h a v e b e e n s t u d i e d by
e l e c t r o n and ion i m p a c t m e t h o d s . F o r e x a m p l e , F i g . 13 showed s o m e s p e c t r a
of e l e c t r o n s e j e c t e d by t h e N 2 m o l e c u l e , a f t e r e x c i t a t i o n by e l e c t r o n i m p a c t .
e + N 2 - N* + e
s»N2 + e ( o b s e r v e d )
The c u r v e s m a r k e d А, В and С w e r e t a k e n at i n c i d e n t e l e c t r o n e n e r g i e s
of 6, 25 and 100 eV, r e s p e c t i v e l y , above the e x c i t a t i o n t h r e s h o l d f o r t h e
p r e i o n i z i n g s t a t e s . Although the s t a t e s n e a r the i o n i z a t i o n l i m i t have been
s e e n p r e v i o u s l y in p h o t o - i o n i z a t i o n e x p e r i m e n t s , - t h o s e which e j e c t e l e c t r o n s
of e n e r g i e s 2 to 3 eV have not been s e e n b e f o r e .
We can d i s t i n g u i s h t h r e e t y p e s of p r e i o n i z i n g s t a t e s of a m o l e c u l e
such as N2:
(i) In the f i r s t type we m a y i m a g i n e t h a t the o u t e r e x c i t e d e l e c t r o n

i s in a R y d b e r g - t y p e o r b i t a l of l a r g e r a d i u s , and e n e r g y - R / n 2 , and that the
IAEA-SMR-12/26, 27 617
M + c o r e i s in i t s ground v i b r a t i o n a l and e l e c t r o n i c s t a t e s , but h a s r o t a t i o n a l

e n e r g y E r o t . Now if E r o t > R / n 2 then the r o t a t i o n a l - e l e c t r o n i c i n t e r a c t i o n
can c a u s e an e n e r g y i n t e r c h a n g e b e t w e e n the r o t a t i o n a l e n e r g y of the c o r e
and the e n e r g y of the o u t e r e l e c t r o n , r e s u l t i n g in the e j e c t i o n of t h i s e l e c t r o n .
The B o r n - O p p e n h e i m e r a p p r o x i m a t i o n d o e s not hold f o r t h e s e s t a t e s of c o u r s e
b e c a u s e the e l e c t r o n i c m o t i o n i s not m u c h f a s t e r than the r o t a t i o n a l m o t i o n
(it can even be s l o w e r ; ), and t h i s c o m p l i c a t e s the t h e o r e t i c a l d e s c r i p t i o n
of t h i s type of p r e i o n i z i n g p r o c e s s .
(ii) In the s e c o n d type the M + c o r e m a y have v i b r a t i o n a l e n e r g y which

i s g r e a t e r than the (negative) e n e r g y of the R y d b e r g e l e c t r o n , and then t h i s
e l e c t r o n m a y be e j e c t e d by an e x c h a n g e of v i b r a t i o n a l and e l e c t r o n i c e n e r g y .
(iii) In the t h i r d type the c o r e m a y have e l e c t r o n i c and v i b r a t i o n a l e n e r g y .

The e j e c t e d e l e c t r o n s would be m o r e e n e r g e t i c than t h o s e r e s u l t i n g f r o m the
o t h e r two t y p e s of p r e i o n i z i n g s t a t e s , and p r o b a b l y it i s t h i s t h i r d type of
s t a t e which h a s b e e n o b s e r v e d in the s p e c t r a of F i g . 13.
O t h e r a u t h o r s have d e a l t with the i n t e r a c t i o n s b e t w e e n d i s c r e t e p r e -

i o n i z i n g s t a t e s of a t o m s and the continua in which they a r e e m b e d d e d ,
so t h i s s u b j e c t n e e d not be t r e a t e d again; we s h a l l d e s c r i b e an i n t e r e s t i n g
c o r r e l a t i o n e f f e c t which we have r e c e n t l y n o t i c e d .
The (2S) 2 1 S s t a t e of h e l i u m h a s an e n e r g y of 57.8 eV and a l i f e t i m e
— 10" 14 s, and n o r m a l l y e j e c t s e l e c t r o n s of e n e r g y 33.2 eV. H o w e v e r ,
when it i s e x c i t e d by e l e c t r o n i m p a c t , and when the i n c i d e n t e l e c t r o n
e n e r g y i s n e a r the t h r e s h o l d f o r e x c i t a t i o n , the e n e r g y of the e j e c t e d
e l e c t r o n s t e n d s to i n c r e a s e . The r e a s o n f o r t h i s a p p e a r s to be that n e a r
the t h r e s h o l d the i n e l a s t i c e l e c t r o n m o v e s away f r o m the e x c i t e d a t o m
r a t h e r slowly, and i s n e a r enough to p e r t u r b the a t o m at the m o m e n t of
i t s d e c a y . The e f f e c t i s quite l a r g e and r e s u l t s in e n e r g y c h a n g e s of up
to about 1 eV.
A c u r i o u s c o n s e q u e n c e of t h i s p e r t u r b a t i o n i s that the m i n i m u m e n e r g y
at which one can e x c i t e t h i s p r e i o n i z i n g s t a t e i s i t s e x c i t a t i o n e n e r g y plus
about 1 eV. In o t h e r w o r d s i t s t h r e s h o l d i s d i s p l a c e d . The s a m e e f f e c t
h a s a l s o b e e n s e e n in o t h e r s t a t e s of h e l i u m and a r g o n .
R E F E R E N C E S
ANDRICK, D. , READ, E.H. (1971) J. Phys. B4 , 389.

BARDSLEY, J . N . , MANDL, F. (1968) Repts. Prog. Phys. 31, 471.
BIRTWISTLE, D . T . , HERZENBERG, A. (1971) J. Phys. В 4, 53.

BONESS, M . J . W . , SCHULZ, G.J. (1970) Phys. Rev. A2_, 2182.
BÖTTCHER, С . , READ, F.H. (1973) to be published.
CARTWRIGHT, D . C . , TRAJMAR, S. , WILLIAMS, W. , HUESTIS, D.L. (1971) Phys. Rev. Lett. 27, 704.
COMER, J . , HARRISON, N.M. (1973) J. Phys. В 6, L70.

COMER, J . , READ, F.H. (1971) J. Phys. В 4, 368.
COMER, J . , READ, F . H . (1972) J. Election. Spect. 1, 3.
CORNEY, A. (1970) Adv. Electron. Electron Phys. 2 9 , 116.

6 1 8 ' READ
EHRHARDT, H . , WILLMANN, К . (1967) Z . Phys. 204 , 4 6 2 .
ELIEZER, I . , TAYLOR, H . S . , WILLIAMS, J . K . (1967) I. C h e m . Phys. 47, 2165.
GRIFFITH, J . S . (1962) The Irreducible Tensor Method for Molecular Symmetry Groups, Englewood Cliffs,
N.J., Prentice-Hall.
HERZBERG, G . (1950) Spectra of Diatomic Molecules, Van Nostrand, Princeton.
HICKS, P . J . , COMER, J . , READ, F . H . (1973) J. Phys. B6, L65,
IM HOF, R . E . , READ, F . H . (1971a) J. Phys. В 4 , 450.
IMHOF, R.E. , READ, F . H . (1971b) J. Phys. B 4, 1063.
IMHOF, R.E. , READ, F . H . (1971c) C h e m . Phys. Lett. 1 1 , 326.
IMHOF, R . E . , READ, F . H . , BECKETT, S . T . (1972) J. Phys. В 5, 896.
INOKUTI, M . (1971) Rev. Mod. Phys. 43, 297.
JOTEZ, G. , COMER, J. , READ, F . H . (1973) J. Phys. В6, 2427.
KING, G . C . M . , ADAMS, A . , READ, F.H.- (1972) J. Phys. В 5, L254.
LASSETTRE, E . N . (1969) C a n . J. C h e m . 47, 1733.
LASSETTRE, E . N . , SKERBELE, A. (1971) J. C h e m . Phys. 54, 1597.
READ, F . H . (1968) J. Phys. B l , 893.
READ, F . H . (1972a) J. Phys. В 5, 255.
READ, F . H . , ANDRICK, D. (1971) J. Phys. В 4, 911.
READ, F . H . , WHITEROD, G . L . (1963) Proc. Phys. Soc. 82, 434.
SCHULZ, C.J. (1962) Phys. Rev. 1 2 5 , 229.
SKERBELE, A . , LASSETTRE, E . N . (1970) J. C h e m . Phys. 53, 3806.

IAEA-SMR-12/40, 41
H E A V Y - P A R T 1С L E COLLISIONS
R. McCARROLL
Laboratoire d'astrophysiqu e,
Université de Bordeaux I,
Talence, France
Abstract
HEAVY-PARTICLE COLLISIONS.
1. Scattering by a centre of force (Quantum theory - summary, classical theory, classical scattering,
eikonal approximation, J. W.K.B, method, high-energy phase shift, validity criteria, calculation of the
scattering amplitude, rainbow effect, halo (glory) effect, orbiting, reduced cross-sections, resonance
processes); 2. Inelastic collisions (general theory, eikonal approximation, eikonal equation - atomic
and molecular representations, expansion in molecular wave functions, solution of the eikonal equation);
3. Particular examples (the H + -H and He+-He systems).
INTRODUCTION
Until r e c e n t l y , the s t u d y of a t o m i c c o l l i s i o n s w a s m a i n l y d i r e c t e d to
the m e a s u r e m e n t o r c a l c u l a t i o n of t o t a l c r o s s - s e c t i o n s . H o w e v e r , the
i n t e r p r e t a t i o n of s u c h m e a s u r e m e n t s in t e r m s of the i n t e r a c t i o n b e t w e e n
the c o l l i d i n g s y s t e m s is p r a c t i c a l l y i m p o s s i b l e s i n c e m a n y d i f f e r e n t
m i c r o s c o p i c p r o c e s s e s m a y c o n t r i b u t e to the t o t a l c r o s s - s e c t i o n . T h i s
s i t u a t i o n h a s b e e n r a d i c a l l y changed with the advent of new e x p e r i m e n t a l
t e c h n i q u e s , m a k i n g it p o s s i b l e to m e a s u r e d i f f e r e n t i a l s c a t t e r i n g c r o s s -
s e c t i o n s f o r e a c h r e a c t i o n c h a n n e l a s a f u n c t i o n of e n e r g y and s c a t t e r i n g
a n g l e . T h e v a s t a m o u n t of e x p e r i m e n t a l s c a t t e r i n g data h a s s t i m u l a t e d
the d e v e l o p m e n t of the t h e o r y e s p e c i a l l y in the l o w - e n e r g y r a n g e f r o m a
f r a c t i o n of an e l e c t r o n volt to t e n s of keV. T h i s new b r a n c h of a t o m i c
collisions is often t e r m e d collision spectroscopy.
T h e p r i n c i p a l a i m of the t h e o r y i s to d e v e l o p a r e l i a b l e m e a n s of
i n t e r p r e t i n g the e x p e r i m e n t a l l y o b s e r v e d s t r u c t u r e of the c r o s s - s e c t i o n
data in t e r m s of the i n t e r a t o m i c i n t e r a c t i o n s . Little d e t a i l e d r e f e r e n c e
t o the p r o b l e m i s to be found in e x i s t i n g t e x t books on c o l l i s i o n t h e o r y .
In the t h e o r y of slow h e a v y p a r t i c l e c o l l i s i o n s u s e is m a d e of the f a c t
t h a t , p r o v i d e d the r e l a t i v e v e l o c i t y of the colliding p a r t i c l e s is c o n s i d e r a b l y
l e s s t h a n the o r b i t a l v e l o c i t y of the bound e l e c t r o n s , the e l e c t r o n i c m o t i o n
f o l l o w s a d i a b a t i c a l l y the n u c l e a r m o t i o n . The colliding s y s t e m m a y then
be d e s c r i b e d by a q u a s i - m o l e c u l e , whose e l e c t r o n i c s t a t e s evolve
a d i a b a t i c a l l y j u s t a s in the B o r n - O p p e n h e i m e r a p p r o x i m a t i o n f o r a s t a b l e
m o l e c u l e w h e r e the e l e c t r o n i c m o t i o n is d e c o u p l e d f r o m the v i b r a t i o n a l
and r o t a t i o n a l m o t i o n of the n u c l e i . T h u s , f o r e x a m p l e , in a c o l l i s i o n
H+ - He the e l e c t r o n s evolve a s the 1 £ s t a t e ofHe-H 1 ", in a c o l l i s i o n He - He
a s the 1 £ g of H e 2 . T h e e l e c t r o n i c e n e r g y , which v a r i e s with the i n t e r -
n u c l e a r d i s t a n c e , c a n t h e n be c o n s i d e r e d a s the p o t e n t i a l e n e r g y t o which
the n u c l e i a r e s u b j e c t . F o r the above e x a m p l e s , the s i t u a t i o n is s i m p l e
s i n c e only one m o l e c u l a r s t a t e is f o r m e d on the a p p r o a c h of t h e two a t o m s
and to the a d i a b a t i c a p p r o x i m a t i o n only e l a s t i c s c a t t e r i n g can o c c u r . In
619
620 McCARROLL
g e n e r a l t h e s i t u a t i o n is m o r e c o m p l e x , s i n c e in m a n y c a s e s s e v e r a l
m o l e c u l a r s t a t e s a r e p o s s i b l e a s the two a t o m s a p p r o a c h . F o r e x a m p l e ,
H e + - H e g i v e s r i s e to two s t a t e s 2 E u 2 £ g , while O - H gives r i s e to 24
d i s t i n c t m o l e c u l a r s t a t e s . T h u s even in an a d i a b a t i c a p p r o a c h r e s o n a n t
p r o c e s s e s of c h a r g e t r a n s f e r o r spin e x c h a n g e m a y o c c u r .
In m o l e c u l a r s p e c t r a , it is w e l l - k n o w n that the B o r n - O p p e n h e i m e r
a p p r o x i m a t i o n b r e a k s down in the vicinity of a c r o s s i n g ( o r , m o r e
c o r r e c t l y , an avoided c r o s s i n g ) of the p o t e n t i a l e n e r g y c u r v e s of two
m o l e c u l a r s t a t e s . T h u s in the collision p r o b l e m , the e l e c t r o n i c motion
and the n u c l e a r m o t i o n w i l l be s t r o n g l y coupled at t h e s e c r o s s i n g s ,
giving r i s e t o l a r g e n o n - a d i a b a t i c e f f e c t s . A l a r g e p a r t of t h i s p a p e r w i l l
t h e r e f o r e be devoted to the influence of s u c h c r o s s i n g s on i n e l a s t i c
transitions.
In p r i n c i p l e , the t h e o r y of a t o m i c c o l l i s i o n s m a y be f o r m u l a t e d in a
p u r e l y q u a n t u m - m e c h a n i c a l f r a m e w o r k . In p r a c t i c e , h o w e v e r , the
c o n d i t i o n s a r e s u c h t h a t the n u c l e a r m o t i o n m a y be a d e q u a t e l y t r e a t e d by
s e m i - c l a s s i c a l m e t h o d s . T h i s leads to c o n s i d e r a b l e s i m p l i f i c a t i o n s and
f a c i l i t a t e s e n o r m o u s l y the p h y s i c a l i n t e r p r e t a t i o n of the e x p e r i m e n t a l
d a t a . E m p h a s i s will t h e r e f o r e be given to the v a r i o u s s e m i - c l a s s i c a l
m e t h o d s u s e d in the t h e o r y . A knowledge of the b a s i c r e s u l t s of q u a n t u m -
m e c h a n i c a l s c a t t e r i n g t h e o r y w i l l be a s s u m e d .
1. S C A T T E R I N G BY A C E N T R E OF F O R C E
1.1. Q u a n t u m t h e o r y - summary
In o r d e r to d e v e l o p the t h e o r y of a t o m - a t o m c o l l i s i o n s it is u s e f u l to
r e c a l l b r i e f l y s o m e of the b a s i c r e s u l t s of the q u a n t u m - m e c h a n i c a l t h e o r y
of p o t e n t i a l s c a t t e r i n g . T h e p r o b l e m of the s c a t t e r i n g of a p a r t i c l e of
m a s s m j by a p a r t i c l e of m a s s m 2 , when the i n t e r a c t i o n V(r) b e t w e e n the
p a r t i c l e s d e p e n d s on the r e l a t i v e c o - o r d i n a t e r = r j - ?2iCan be r e d u c e d
t o the p r o b l e m of a p a r t i c l e with r e d u c e d m a s s m = m i m j / l m i +П12) in
a p o t e n t i a l field V ( r ) . It i s convenient to u s e i n s t e a d of a t i m e - d e p e n d e n t
d e s c r i p t i o n , the e q u i v a l e n t s t a t i o n a r y p r o b l e m . In the s t a t i o n a r y d e s c r i p -
tion, the s c a t t e r i n g p r o b l e m c o n s i s t s of the e v a l u a t i o n of the c u r r e n t
of s c a t t e r e d p a r t i c l e s a s a function of the c u r r e n t of i n c o m i n g p a r t i c l e s .
The S c h r o d i n g e r e q u a t i o n is t h e n
[ V 2 + k 2 ]<Mrl = f r У(?Ж?) (bl)
where k2 = 2mE/ti2.
P r o v i d e d the p o t e n t i a l V(r) f a l l s off m o r e r a p i d l y than 1 / r a s r-» oo,
the p a r t i c l e s m o v e in a f o r c e - f r e e field f o r l a r g e r and the c o r r e s p o n d i n g
wave-function is
фа(?) = e x p ( i k a . ? ) ; k^ = k 2 (1.2)
s a t i s f y i n g (1.1) without i t s r i g h t - h a n d s i d e . The w a v e - v e c t o r k a i s r e l a t e d

t o the m o m e n t u m p of the r e l a t i v e motion by p = h k a . The f u n c t i o n фа(г)
IAEA-SMR-12/26, 27 621
i s n o r m a l i z e d s u c h that the p a r t i c l e - f l u x d e n s i t y be e q u a l to the v e l o c i t y

of r e l a t i v e m o t i o n
Г= -ф^ф*) = (1.3)
T h e p r o b l e m c o n s i s t s in finding t h o s e s o l u t i o n s of E q . ( l . l ) which c a n be
w r i t t e n a s a s u p e r p o s i t i o n of the p l a n e wave (1.2) and s c a t t e r e d w a v e s
c o m i n g f r o m the c e n t r e of f o r c e . Using the G r e e n ' s f u n c t i o n of the o p e r a t o r
of the l e f t - h a n d s i d e of (1.1) the s o l u t i o n of (1.1) m a y be w r i t t e n a s
</,(?)= ф а (г) + f G 0 ( r : ? ) ^ V ( ? ) i K ? ) d ? ' (1.4)
w h e r e G o ( r , r 1 ) s a t i s f i e s the e q u a t i o n
[V 2 + k 2 ] G 0 ( ? , ? ' ) = 6 (?-?•) (1.5)
It m a y be shown that the s o l u t i o n of (1.5) c o r r e s p o n d i n g to an outgoing

wave is
„ exp ik r - r ' ,„ „
At l a r g e d i s t a n c e s , we m a y w r i t e
к I r - r ' I ^ k r - k b • r1 (1.7)
where
kb = k r / r
s o t h a t the a s y m p t o t i c f o r m of (r) is
-> p ikr
(1-8)
where
f
k(e'<r) = (1-9)
T h e f u n c t i o n fj'(e,<f>) is called the s c a t t e r i n g a m p l i t u d e . It d e p e n d s on the

e n e r g y of r e l a t i v e m o t i o n , on the angle b e t w e e n the v e c t o r s ica and íTb
and on V.
T h e s c a t t e r i n g is c h a r a c t e r i z e d by the d i f f e r e n t i a l s c a t t e r i n g c r o s s -
s e c t i o n d o / d Q which d e t e r m i n e s the r a t i o of the n u m b e r of p a r t i c l e s
s c a t t e r e d p e r unit t i m e into an e l e m e n t of solid angle d£7 = s i n в de dtf> to
the flux d e n s i t y of i n c o m i n g p a r t i c l e s . C a l c u l a t i n g the r a d i a l flux d e n s i t y
f r o m (1.3) it is t r i v i a l to e s t a b l i s h that
da i 12
=
ĎŇ LFR(E^)L (1Л°)
622 McCARROLL
P a r t i a l - w a v e method
If the p o t e n t i a l V(r) is s p h e r i c a l l y s y m m e t r i c , the a n g u l a r m o m e n t u m

is an i n t e g r a l of m o t i o n . S t a t e s c o r r e s p o n d i n g to d i f f e r e n t v a l u e s of a n g u l a r
m o m e n t u m can be c o n s i d e r e d independently. Taking the z - a x i s in the
d i r e c t i o n k a of the i n c i d e n t p a r t i c l e , the wave f u n c t i o n ф{r) m a y be
expanded a s
ф(г) = У r F { (r) P{ (cos 6) (1.11)

8=0
w h e r e the r a d i a l f u n c t i o n F { (r) s a t i s f i e s the e q u a t i o n
J L . Ш±11_ 2mV(r) | ka F,(r) = 0 (1.12)

dr2 г2 ti^
T h e wave f u n c t i o n ф m u s t be finite at r = 0 s o t h a t F { (r) m u s t s a t i s f y the

condition
Ft (0) = 0 (1.13)
The a s y m p t o t i c f o r m of F j (r) m a y be w r i t t e n a s
F« (r) — a ( sin (kr - \ Hit + 61) (1.14)

r~> «
w h e r e 6{ is d e f i n e d a s the p h a s e s h i f t .
C o m p a r i n g (1.15) with (1.8) it is e a s i l y e s t a b l i s h e d that
f (0,<p) = V 0Ti7 ( e 2 i ó í - 1) (2í + 1) P { ( c o s 0 ) (1.15)

_ 2ik
{=0
T h e s o l u t i o n of the p o t e n t i a l s c a t t e r i n g p r o b l e m m a y thus be obtained

to any r e q u i r e d d e g r e e of a c c u r a c y , by solving the r a d i a l equation (1.12)
n u m e r i c a l l y t o c a l c u l a t e the p h a s e s h i f t s . H o w e v e r , in p r a c t i c e , the
d i r e c t n u m e r i c a l solution of (1.12) i s convenient only if a s m a l l n u m b e r
of p a r t i a l w a v e s c o n t r i b u t e s e f f e c t i v e l y to the s c a t t e r i n g a m p l i t u d e . Such
is the c a s e f o r e l e c t r o n s c a t t e r i n g by a t o m s . In the c a s e of a t o m - a t o m
s c a t t e r i n g , the e f f e c t i v e n u m b e r of p a r t i a l w a v e s which c o n t r i b u t e to
f (0, tfi) m a y r u n to s e v e r a l t h o u s a n d s . A d i r e c t s o l u t i o n is t h e r e f o r e not
a l w a y s p r a c t i c a l . H o w e v e r , when this s i t u a t i o n o c c u r s , the d y n a m i c a l
s y s t e m i s w e l l d e s c r i b e d by the s e m i - c l a s s i c a l a p p r o x i m a t i o n . It is
t h e r e f o r e of i n t e r e s t to i n v e s t i g a t e s o m e of the s p e c i a l m e t h o d s which
have b e e n d e v e l o p e d in the s e m i - c l a s s i c a l f r a m e w o r k .
1.2. C l a s s i c a l t h e o r y
In o p t i c s , w h e n the w a v e l e n g t h of light is s m a l l c o m p a r e d with the

d i s t a n c e o v e r which the r e f r a c t i v e index c h a n g e s a p p r e c i a b l y , it is p o s s i b l e
t o d e f i n e r a y s which obey the l a w s of g e o m e t r i c a l o p t i c s . By analogy, if
IAEA-SMR-12/26, 27 623
the w a v e l e n g t h (h/p) of a p a r t i c l e i s s u f f i c i e n t l y s h o r t c o m p a r e d with the

d i s t a n c e in which the p o t e n t i a l c h a n g e s a p p r e c i a b l y , it i s p o s s i b l e to d e f i n e
p a r t i c l e t r a j e c t o r i e s d e s c r i b e d by the l a w s of c l a s s i c a l m e c h a n i c s . The
s e m i - c l a s s i c a l a p p r o x i m a t i o n , which is i n t e r m e d i a t e in c h a r a c t e r b e t w e e n г
p u r e l y c l a s s i c a l and a p u r e q u a n t u m t r e a t m e n t , e n a b l e s us to take a c c o u n t
of the q u a n t a l c h a r a c t e r i s t i c s of a d y n a m i c a l s y s t e m in t h e s e c a s e s w h e r e
the s h o r t - w a v e l e n g t h condition is v a l i d , without having to solve the
Schrödinger equation.
F o r p o t e n t i a l s c a t t e r i n g , the s h o r t - w a v e l e n g t h condition i s that
ka » 1, w h e r e a r e p r e s e n t s the r a n g e of the p o t e n t i a l . F o r c l a s s i c a l
conditions to be valid the s c a t t e r i n g angle is w e l l d e f i n e d ; in o t h e r w o r d s ,
the u n c e r t a i n t y Д 0 in the s c a t t e r i n g angle m u s t be s m a l l c o m p a r e d with 0.
T h e u n c e r t a i n t y in the t r a n s v e r s e m o m e n t u m i m p a r t e d to the s c a t t e r e d
p a r t i c l e , Д р is f r o m H e i s e n b e r g ' s u n c e r t a i n t y p r i n c i p l e of the o r d e r (ft/a).
T h e c o r r e s p o n d i n g u n c e r t a i n t y in the angle of s c a t t e r i n g is
(1.16)
4
p ka '
and t h e r e f o r e f o r c l a s s i c a l conditions to apply

б » 1/ka (1-17)
If V i s the m e a n a v e r a g e p o t e n t i a l in the r e g i o n 0 < r < a , the m o m e n t u m

t r a n s f e r ftK a c q u i r e d by the s c a t t e r e d p a r t i c l e in the t r a n s v e r s e d i r e c t i o n
i s of t h e o r d e r
h K . f U f (1.18)
T h e angle of s c a t t e r i n g at s m a l l a n g l e s is thus a p p r o x i m a t e l y
T h e i n e q u a l i t y Д6 « в can t h e r e f o r e be e x p r e s s e d as
1
S » T1-20'
1.3. C l a s s i c a l s c a t t e r i n g
F o r a s p h e r i c a l l y s y m m e t r i c p o t e n t i a l , the motion t a k e s place in a

p l a n e . The L a g r a n g i a n is
ç f = S . (ř2 + r2ý2) _ v ( r ) (1.21)
w h e r e ( r , u) a r e the plane p o l a r c o - o r d i n a t e s of the p a r t i c l e . Since u is a

c y c l i c c o - o r d i n a t e the a n g u l a r m o m e n t u m
L = = mr2ij (1.22)
дь)
624 McCARROLL
i s a c o n s t a n t of the m o t i o n . The total e n e r g y E is c o n s e r v e d so that
2
T
(1.23)
E = I m ( ř 2 + r 2 ù 2 ) + V(r) = \ m ř 2 + + Vir)
is a constant. E q u a t i o n (1.23) y i e l d s 1/2

dr
dt~ JR I E - V ( R ) - 2 m L 2 (1.24)
r
w h i c h on i n t e g r a t i o n y i e l d s
(1.25)
w h e r e to i s a c o n s t a n t of i n t e g r a t i o n . F r o m e q u a t i o n s (1.22) and (1.24),

it m a y be s i m p l y s h o w n t h a t
i
f dr - Цz { i - [E - V ( r ) ] - (1.26)
J mr [ m m^r' |
:
o
г я Г ь211/2
- J d r ^ { 2 m [ E - V ( r ) ] - ^ } (1.27)
w h e r e t h e c o n s t a n t of i n t e g r a t i o n i s c h o s e n s o t h a t и = 0 at r = r 0 , the
d i s t a n c e of c l o s e s t a p p r o a c h . T h i s i s d e t e r m i n e d by the c o n d i t i o n ř = 0,
s o t h a t r 0 i s the r o o t of
L2
2m [E - V ( r 0 ) ] = (1.28)
T h e a n g l e a b e t w e e n the a s y m p t o t e s of the o r b i t i s t h e n
or = - 2 J dr j 2m [E - V ( r ) ] - ^ j (1.29)
Го
The deflection angle 0 is defined as
© = 7Г - a (1.30)
If G l i e s in the i n t e r v a l 0 < 0 < n and if 0 i s a m o n o t o n i e f u n c t i o n of L ,

t h e n 0 c a n be i d e n t i f i e d w i t h the s c a t t e r i n g a n g l e в. In g e n e r a l the d e f l e c -
t i o n a n g l e m a y t a k e a n y v a l u e in the i n t e r v a l -<x> с ©< v. T h e s c a t t e r i n g
a n g l e w h i c h i s d e f i n e d t o l i e in t h e i n t e r v a l 0 < б < ж is t h e n
в = ± 0 + 2тг n (1.31)
w h e r e n is an i n t e g e r o r z e r o .
lAEA-SMR-12/40, 41 625
T h e d i f f e r e n t i a l s c a t t e r i n g c r o s s - s e c t i o n is obtained by c o n s i d e r i n g
the s c a t t e r i n g of a u n i f o r m b e a m of p a r t i c l e s of v e l o c i t y v. If N p a r t i c l e s
c r o s s the unit a r e a n o r m a l t o the b e a m p e r unit t i m e , then the n u m b e r
p e r unit t i m e , with a n g u l a r m o m e n t u m b e t w e e n L and L + d L , is equal to
the n u m b e r p e r unit t i m e with i m p a c t p a r a m e t e r s b e t w e e n b and b + db,
w h e r e b = L / m v and is given by
2TrNbdb = 2 7 r N L d L / m 2 v 2 (1.32)
T h e n the n u m b e r of p a r t i c l e s s c a t t e r e d p e r unit t i m e b e t w e e n 0 and

0 + de is
2ttNL dL
I= m 2 v2 de (1.33)
de
w h e r e L(0) is given by E q s (1.29), (1.30) and (1.31). T h e d i f f e r e n t i a l

c r o s s - s e c t i o n dcr/dfi i s then
do = L dL 1
(1.34)
dfi m2v2 de sin (
If t h e r e i s m o r e than one value of L s a t i s f y i n g (1.29) f o r a given 0, the

c r o s s - s e c t i o n is the s u m of c o n t r i b u t i o n s f r o m e a c h b r a n c h of the f u n c t i o n
do Г L2 i dL 1
(1.35)
di7 _ m v2 de j s i n 0
1.4. T h e e i k o n a l a p p r o x i m a t i o n
In o r d e r to i n v e s t i g a t e the c l a s s i c a l l i m i t of the S c h r ö d i n g e r e q u a t i o n ,
t h e wave f u n c t i o n i s w r i t t e n in the f o r m
Ф Й = eiS(rT/fi (1.36)
S u b s t i t u t i o n into the S c h r ö d i n g e r e q u a t i o n (1.1) y i e l d s
[ - i f t V 2 S + (VS) 2 ] = E - V(r) (1.37)
T h e c l a s s i c a l l i m i t i s found by taking the l i m i t ft 0.

In t h i s l i m i t , S = S 0 ( r ) w h e r e
— (VS 0 ) 2 = E --V(r) (1.38)
w h i c h i s the c l a s s i c a l H a m i l t o n - J a c o b i e q u a t i o n if Sq(t) is identified with

H a m i l t o n ' s c h a r a c t e r i s t i c f u n c t i o n . The t r a j e c t o r y of a p a r t i c l e in
c l a s s i c a l m e c h a n i c s being n o r m a l to the s u r f a c e s of c o n s t a n t So, it is
s t r a i g h t f o r w a r d to d e t e r m i n e S 0 f r o m Eq.(1.38) by i n t e g r a t i o n of VSo
along the c l a s s i c a l t r a j e c t o r y . By a n a l o g y with o p t i c s Eq.(1.38) is r e f e r r e d
to a s the e i k o n a l e q u a t i o n .
626 McCARROLL
If now S 0 ( r ) is s u b s t i t u t e d into (1.36), the r e s u l t i n g wave f u n c t i o n i s

d e f i n e d a s the e i k o n a l wave f u n c t i o n . The u s e of this wave f u n c t i o n in the
i n t e g r a l equation f o r the s c a t t e r i n g a m p l i t u d e f o r m s the b a s i s of the e i k o n a l
approximation.
F o r m a n y c a s e s of i n t e r e s t in heavy p a r t i c l e c o l l i s i o n s , s c a t t e r i n g
i s confined to s m a l l a n g l e s and the t r a j e c t o r i e s d i f f e r l i t t l e f r o m s t r a i g h t
l i n e s p a r a l l e l to the i n c i d e n t d i r e c t i o n . Choosing the c o - o r d i n a t e s y s t e m
a s in s e c t i o n 1.1. with Й a unit y e c t o r p a r a l l e l to the z - a x i s and defining
b a s a v e c t o r p e r p e n d i c u l a r to 1? and of m a g n i t u d e e q u a l to the c l a s s i c a l
i m p a c t p a r a m e t e r , the o r b i t is defined by
r = b + zŘ (1.39)
with b • £ = 0.
T o t h i s a p p r o x i m a t i o n z = vt and the e i k o n a l equation (1.38) which
r e d u c e s to
l2
1
^ 4( b - z ) = E - V(r) (1.41)
2m 9z
h a s the s o l u t i o n
S 0 (t>, z) = / {2m [E - V(r)]} 1 / 2 dz + c o n s t a n t (1-42)
Now the wave f u n c t i o n ф{r) m u s t a p p r o a c h a plane wave a s z -» -oo. In

other words
S0(z) ~ hkz (1.43)
T h e a p p r o x i m a t e s o l u t i o n (1.42) does not have the c o r r e c t a s y m p t o t i c

b e h a v i o u r of a s c a t t e r i n g wave f u n c t i o n , in that it d o e s not d e s c r i b e o u t -
going s p h e r i c a l w a v e s at l a r g e r . H o w e v e r , it d o e s r e p r e s e n t the wave
f u n c t i o n w e l l in the r e g i o n w h e r e V is l a r g e . Imposing the condition (1.43)
we find .
z
S 0 ( b , z) = hkz-L + / {2m[E - V(r)]}1/2 dz (1-44)
w h e r e z i is a r b i t r a r i l y l a r g e . F o r l a r g e v a l u e s of m o m e n t u m ftk, (1.44)
m a y be a p p r o x i m a t e d by
S0(b,z) = hkz - g J V(r)dz (1.45)
T h e s c a t t e r i n g a m p l i t u d e i s then
fk(e.«P) = - ^ J d r e"lk ' 1

U(r) exp i k . ? - ^ / u ( r ) d z ]
IAEA-SMR-12/26, 27 627
where
?m
U(r) = V(r) (1.46)
I n t r o d u c i n g the m o m e n t u m t r a n s f e r
q = к - к' (1.47)
we m a y w r i t e
e x p i (к • r - к' • r) - e x p iq (b + kz) (1.48)
Since |iî| = |íc' | , the m o m e n t u m t r a n s f e r i s a l m o s t p e r p e n d i c u l a r to к

f o r s m a l l s c a t t e r i n g a n g l e s , s o that to a good a p p r o x i m a t i o n
q • к = k ( l - cos 6) Ä i к б2 (1.49)
In r e a l i t y , (1.49) i s not a s u p p l e m e n t a r y a p p r o x i m a t i o n . Its v a l i d i t y i s

p r o b a b l y m u c h w i d e r t h a n is the e i k o n a l a p p r o x i m a t i o n with s t r a i g h t - l i n e
t r a j e c t o r i e s (1.42). In addition the t e r m exp ( i q . It z) m a y be r e p l a c e d by 1
f o r a n g l e s such that ô2 ka « 1. (The m a j o r c o n t r i b u t i o n to the i n t e g r a l (1.46)
c o m e s f r o m t h e r e g i o n r < a.) T h e r e f o r e
2n
fk(0) = d < p b d b dzei? ?U(r)exp dz
"ï7 I / J ' {" ik J ' u(r)|
2tt « Л
á<P
Ш I /bdbe'fff E X P D 2 U 1 (1.51)
_ I " È / W } -
о о
Since the p o t e n t i a l U(r) i s s p h e r i c a l l y s y m m e t r i c , the i n t e g r a t i o n o v e r

<p m a y be i m m e d i a t e l y c a r r i e d out
J d
T h e e i k o n a l a p p r o x i m a t i o n is e q u a l l y valid f o r a b s o r p t i v e p o t e n t i a l s . In
this case x becomes complex.
628 McCARROLL
1.5. T h e J . W . K . В . m e t h o d
In t h i s m e t h o d , the p h a s e s h i f t s 6 f a r e c o m p u t e d f r o m a s e m i -
c l a s s i c a l s o l u t i o n of the r a d i a l e q u a t i o n s (1.4). T h e m a i n a d v a n t a g e of t h i s
m e t h o d is that the a n g u l a r m o m e n t u m f u n c t i o n s a r e t r e a t e d e x a c t l y . T h e
s e m i - c l a s s i c a l p h a s e s h i f t s m a y then be u s e d d i r e c t l y in the p a r t i a l - w a v e
s e r i e s (1.6) o r in an i n t e g r a l e x p r e s s i o n of the type (1.53).
B e c a u s e of the s i n g u l a r i t y in Eq.(1.4) at r = 0, it i s convenient to
t r a n s f o r m the equation by the following s u b s t i t u t i o n s
x = log r g. = r ~ 1 / 2 f ( r ) (1.55)
yielding
d2g
^l+F(x)g =0 (1.56)
where
F(x) = e 2 x [ k 2 - U - e " 2 x (Í + 1) 2 ] (1.57)
The v a r i a b l e x now e x t e n d s f r o m - » t o and F(x) is f r e e f r o m

s i n g u l a r i t i e s . We s e t
g(x) = e i S ( x ' / h (1.58)
S u b s t i t u t i o n of (1.58) in (1.56) gives
çfS ++ f dS Y = F ( x )
t1-59)
Expanding
S(x) = So (x) + h S x ( x ) + h 2 S 2 ( x ) + ... (1.60)
s u b s t i t u t i n g in (1.59) and e q u a t i n g the c o e f f i c i e n t s of e a c h p o w e r of h

yields g
( t o <«•>
2
- ' S K f O - S
I n t e g r a t i n g (1.61) we find
S0 = ± J [F(x)]1/2dx (1.64)
Using (1.64) in (1.62) t h e n y i e l d s
Sj(x) = i log | F ( x ) | l / 4 (1.65)

I A E A - S M R - 1 2 / 2 6 , 27 629
N e g l e c t i n g S 2 and h i g h e r t e r m s , the m o s t g e n e r a l solution f o r the c a s e

F(x) p o s i t i v e is obtained a s
.(x) = |F(x) |" 1 / 4 -jA exp J dx'F(x')1/2 + В exp dx F

"h J ' (x')1/2
(1.66)
and f o r F(x) n e g a t i v e
.(x) = |F(x) |" 1 / 4 -I С exp i J dx' |F(X')| I / 2

+ Dexp j - i J dx 1 | F ( x ' ) | 1 / 2
(1.67)
w h e r e A, B, C, D a r e a r b i t r a r y c o n s t a n t s .
At s o m e point x = x 0 F(x) will p a s s t h r o u g h z e r o .
F(x) < 0 for x < x 0
> 0 X > X ,
T h e n the s o l u t i o n f o r l a r g e n e g a t i v e x, s a t i s f y i n g the b o u n d a r y condition

g(x) -» 0 a s x -> - oo t is
.(x) = |F(X)|"1/4 D exp | - I J dx 1 | F ( x ' ) j 1 / 2 I (1.68)
In the v i c i n i t y of x = t x 0 , the s e m i - c l a s s i c a l solution is i n v a l i d , s i n c e

h i g h e r t e r m s of the s e r i e s S n cannot in p r i n c i p l e be n e g l e c t e d . H o w e v e r ,
writing
F(x) « A (x - x 0 ) (1.69)
a r o u n d x = x 0 , the q u a n t a l solution of Eq.(1.56) in t h i s r e g i o n m a y be

s i m p l y o b t a i n e d . Making u s e of the connection f o r m u l a (cf. Schiff
' Q u a n t u m M e c h a n i c s ' ) it can be e s t a b l i s h e d that the r e q u i r e d solution
f o r x » x 0 t h a t j o i n s the solution f o r x < x 0 is
. (x) = F ( x ) " 1 / 4 s i n J | F ( x ' ) | 1 / 2 dx + я / 4 (1.70)
R e t u r n i n g to the o r i g i n a l v a r i a b l e r , the r a d i a l wave f u n c t i o n is then

obtained a s
f j ( r ) = c o n s t a n t X F ( r ) " 1 / 4 sin J F ( r ' ) 1/i2 d r ' + 7t/4 (1.71)
where
F ( r ) = k 2 - U(r) - (I + \Ý j r 2 (1.72)
630 McCARROLL
Since l i m F(r)" 1 / Í 4 is a c o n s t a n t , it f o l l o w s that the p h a s e s h i f t Ь ц m a y
be i d e n t i f i e d a s
à, = J [ F i / 2 ( r ' ) - k ] d r ' + ( i +è) I - k r 0 (1.73)
T h e e x p r e s s i o n (1.73) is a c c u r a t e f o r l a r g e v a l u e s of I. F o r l a r g e SI,
the a n g u l a r m o m e n t u m i s given by
%
L =h (Í +1) h {.£ + i )
so t h a t we m a y w r i t e
1 1/2
1 Ltt
= 2m ( E - V ( r ) ) - - khV d r + — - k r 0 (1.74)
h
Го
which is e q u i v a l e n t to
Го
C o m p a r i n g with Eq.(1.29) we s e e that
* Jt • I 6
^
w h e r e © i s the c l a s s i c a l d e f l e c t i o n a n g l e .
Defining
ô{ = J Krdr - J K0dr (1.79)

го r;
» / (K r - K 0 ) d r (1.80)
1.6. H i g h - e n e r g y p h a s e s h i f t
F o r l a r g e I ( l a r g e i m p a c t p a r a m e t e r s ) we m a y a p p r o x i m a t e Eq.(1.79)
by e x p a n d i n g (K r - K 0 ) in p o w e r s of 1 / K 0 - T h e n r e t a i n i n g only the leading
t e r m we have
IAEA-SMR-12/26, 27 631
1/2
2mV
6» = Kr 1 - M dr (1.81)
ft2 К 2
rV r
_2L f ( ) d r (1.82)
h2k J J r 2 - b2
b
Setting z 2 = r 2 - b 2 we o b t a i n
m
m l 1 I tT / \ i
6 2
« * - ři tt V
(r) dZ (1.83)
k 29
(1.84)
6
« =
" 4k J - U(r) dZ
T h e p h a s e s h i f t obtained in this w a y i s i d e n t i c a l to the p h a s e s h i f t

a p p e a r i n g in the e i k o n a l a p p r o x i m a t i o n . H o w e v e r , the d e r i v a t i o n by the
e i k o n a l m e t h o d is m o r e g e n e r a l a s it is valid f o r a n i s o t r o p i c p o t e n t i a l s .
1.7. V a l i d i t y c r i t e r i a
T h e r e g i o n s in which the v a r i o u s a p p r o x i m a t i o n s a r e b e s t s u i t e d f o r
c a l c u l a t i n g p h a s e s m a y be s u m m a r i z e d in the f o r m of a d i a g r a m . T h e
n u m b e r of p a r t i a l w a v e s which c o n t r i b u t e e f f e c t i v e l y to the c r o s s - s e c t i o n
in (1.16) i s of the o r d e r
ka (1.85)
w h e r e a r e p r e s e n t s the r a n g e of the p o t e n t i a l . Defining
V V (r) dz (1.86)
2b
the a b s o l u t e value of the a v e r a g e p o t e n t i a l is
1
Щ = (1.87)
It i s t h e r e f o r e m e a n i n g f u l to plot | v | / E a g a i n s t £. The quantity | v | / E v a r i e s

f r o m 1 to 10"3 and £ f r o m 1 to 10 3 . The p h a s e 26 ц i s c o n s t a n t along the d i a g o n a l s
and r u n s f r o m 10"3 to 10 3 . The |v| / Е , £ plane is divided into 2 h a l v e s , the
dividing line b e i n g s e t a r b i t r a r i l y at £ = 30. F o r £ < 30, c o r r e s p o n d i n g to s m a l l
v a l u e s of k a , a r i g o r o u s q u a n t u m - m e c h a n i c a l s o l u t i o n is p r o b a b l y to be
p r e f e r r e d . A s i m p l i f i c a t i o n is p o s s i b l e n e v e r t h e l e s s when 6{ is s m a l l ,
f o r the B o r n a p p r o x i m a t i o n i s then v a l i d . F o r £ i 30, the s e m i - c l a s s i c a l
a p p r o x i m a t i o n i s v a l i d . In t h i s c a s e , f o r l a r g e 6с , the c l a s s i c a l t h e o r y i s
632 McCARROLL
quantum mechanical semiclassical

phase shifts phase shifts
— f-A
FIG. 1. Validity diagram for the calculation of scattering phase shifts (Pauly and Toennies (1965)).
v a l i d w h i l e f o r V / E < 1 t h e p h a s e e x p r e s s i o n s i m p l i f i e s t o the h i g h - e n e r g y
a p p r o x i m a t i o n , the b o u n d a r i e s in the f i g u r e a r e s o m e w h a t a r b i t r a r y a n d
it i s l i k e l y t h a t s o m e of t h e t h e o r i e s h a v e a l a r g e r r a n g e of v a l i d i t y t h a n
i s i n d i c a t e d (cf. F i g . l ) .
1.8. C a l c u l a t i o n of t h e s c a t t e r i n g a m p l i t u d e
T h e s c a t t e r i n g a m p l i t u d e m a y be c a l c u l a t e d d i r e c t l y by u s i n g the
e x p r e s s i o n f o r 6ц in ( 1 . 1 5 ) . In p r a c t i c e t h i s p r o c e d u r e i s q u i t e l e n g t h y
s i n c e a l a r g e n u m b e r of v a l u e s of i c o n t r i b u t e to the s u m m a t i o n in (1.15)
but if it i s d e s i r e d to h a v e the s c a t t e r i n g a m p l i t u d e f o r a l l a n g l e s t h e
d i r e c t m e t h o d i s to be p r e f e r r e d . It i s n e v e r t h e l e s s i n s t r u c t i v e t o e x a m i n e
a n u m b e r of s i m p l i f i c a t i o n s u n d e r c e r t a i n c i r c u m s t a n c e s .
T h u s , f o r e x a m p l e f o r SL > 1 / s i n Ö, we m a y r e p l a c e P ř (cos 6) by the
l e a d i n g t e r m of i t s a s y m p t o t i c e x p a n s i o n in SL
P e (cos в) ~ (SL s i n e ] " 1 / 2 s i n [ (SL + | ) 6+ тг/4] (1.88)

I A E A - S M R - 1 2 / 2 6 , 27 633
In the p a r t i a l - w a v e s e r i e s f o r f(0), the t e r m not involving the p h a s e s h i f t

m a y be s u m m e d
ec
! ^T (2£ + 1) Pp (cos 0) Pp (1) = 6 (cos 6 - 1 ) (1.89)
«=o
u s i n g the c l o s u r e r e l a t i o n f o r the L e g e n d r e p o l y n o m i a l s . T h i s t e r m only

c o n t r i b u t e s to the f o r w a r d d i r e c t i o n and i s t h e r e f o r e o m i t t e d (in any c a s e
we s u p p o s e в >1/1.). R e p l a c i n g the s u m m a t i o n o v e r £ by an i n t e g r a t i o n
and u s i n g (1.88) we obtain
-1/2
7Г sin E
'<«> = * 2k J (i+5) 1
/ 2
[ e 1
^ - eiTi- ] di (1.90)
where
rj* = 26, ± (Í + i ) 0 ± тг/4 (1.92)
T h e m a j o r c o n t r i b u t i o n .to this i n t e g r a l c o m e s f r o m r e g i o n s in which

9 r t + / d l , drj~/d.H or both a r e z e r o ; that is f r o m the r e g i o n s of s t a t i o n a r y
p h a s e . We m a k e u s e of the c l a s s i c a l e q u i v a l e n c e r e l a t i o n
2 If- = e (1.93)
t h e n the condition
= 0
f f (b94>
i m p l i e s б = + ©.
In o t h e r w o r d s , the d o m i n a n t c o n t r i b u t i o n to f(0) a r i s e s f r o m the
s a m e r e g i o n © a s in the c l a s s i c a l l i m i t .
F o r e x a m p l e , if we c o n s i d e r the c a s e of a t y p i c a l p o t e n t i a l in i o n - a t o m
o r a t o m - a t o m s c a t t e r i n g , with a m i n i m u m f o r s o m e value of r , the V(r)
c u r v e shown in F i g . 2 is o b t a i n e d .
At s o m e s e l e c t e d v a l u e of the e n e r g y the p o t e n t i a l g i v e s r i s e to a
d e f l e c t i o n f u n c t i o n ©(b) of the f o r m shown in F i g . 3 . T h e n , when the
m a x i m u m n e g a t i v e v a l u e of © h a s the m a g n i t u d e 6m < u,
в < 9m r)+ h a s two p o i n t s of s t a t i o n a r y p h a s e ,

77~ h a s one point of s t a t i o n a r y p h a s e ,
6 > 6 m ri+ h a s no point of s t a t i o n a r y p h a s e ,
г)" h a s one point of s t a t i o n a r y p h a s e .
In the c a s e of a p u r e l y r e p u l s i v e p o t e n t i a l the d e f l e c t i o n f u n c t i o n is a l w a y s
p o s i t i v e , s o t h a t t h e r e is only one point of s t a t i o n a r y p h a s e (in rj") f o r a l l
s c a t t e r i n g a n g l e s . A d d i t i o n a l c o n t r i b u t i o n s in both c a s e s w i l l of c o u r s e
a r i s e if j© I > 7Г.
634 McCARROLL
Vir)
FIG. 2. Typical potential energy curve.
FIG. 3. Typical variation of the deflection function 9 as a function of impact parameter b.
If a l l the r e g i o n s of s t a t i o n a r y p h a s e a r e w e l l s e p a r a t e d then the

s e m i - c l a s s i c a l s c a t t e r i n g a m p l i t u d e f s c ( 6 ) is s i m p l y a s u m of t e r m s ,
c o r r e s p o n d i n g to the n u m b e r of points of s t a t i o n a r y p h a s e .
Let u s a s s u m e t h a t SL = £o i s a point of s t a t i o n a r y p h a s e . T h e n c l o s e to io
**(£) = г,Ц£0) = è i 7 i M ( i 0 ) ( j ř - i 0 ) 2 + ... (1.95)
Using E q s (1.92) and (1.93) it i s e a s i l y s e e n t h a t
"4"<'o> = Ш (1.96)
T h e s c a t t e r i n g angle в being always t a k e n p o s i t i v e , the s i g n to be

u s e d in (1.94) i s thus u n i q u e l y d e t e r m i n e d (© is p o s i t i v e f o r a r e p u l s i v e
p o t e n t i a l , n e g a t i v e f o r a n a t t r a c t i v e one).
T h e c o n t r i b u t i o n to f s c (6) a r i s i n g f r o m the r e g i o n a r o u n d SL = SLo
i s then
I A E A - S M R - 1 2 / 2 6 , 27 635
f
sc(0) = k(2
я-sin6)i/2 I (^+5)1/2exp{l ir,*"(i0)(jí-je0)2}djeexp[ir)*(í0)]
o
(1.97)
•I 1 / 2
io exp [ir)±(í0)] (1.98)
к L ini"(ío)sine.
T
L
d b lI1 / 2
D L
6
iil^íol-irM}
z (1.99)
m v^ s i n (
^ Y " e (1.100)
w h e r e d a / d í 2 i s the c l a s s i c a l c r o s s - s e c t i o n and ß0 = r/±(S>0) - 7t/4.

If only one p o i n t of s t a t i o n a r y p h a s e e x i s t s t h e n the c r o s s - s e c t i o n is
i d e n t i c a l t o the c l a s s i c a l r e s u l t . But if s e v e r a l p o i n t s of s t a t i o n a r y p h a s e
e x i s t ' , a d i f f e r e n t r e s u l t i s o b t a i n e d due to the p r e s e n c e of the p h a s e
e x p i ß 0 in (1.100).
L e t u s a s s u m e the p o i n t s of s t a t i o n a r y p h a s e o c c u r at i = SL ;,
i = 1, ... n . C o r r e s p o n d i n g t o e a c h SLj t h e r e w i l l e x i s t a (da/d£7)j and a
S; d i s t i n c t . T h e d i f f e r e n t i a l c r o s s - s e c t i o n i s t h e n
1/2
dg dff
(1.101)
dfi dfi
T h e p r e s e n c e of the p h a s e f a c t o r s l e a d s to i n t e r f e r e n c e e f f e c t s . T h u s if
t h e r e a r e t w o p o i n t s of s t a t i o n a r y p h a s e i j , &2 t h e e x p r e s s i o n (1.101)
m a y be w r i t t e n a s
T h e c r o s s - s e c t i o n w i l l t h u s o s c i l l a t e a s a f u n c t i o n of 6. T h e i n c r e m e n t
6 0 f r o m a m a x i m u m to a m i n i m u m
È{6) ( 1 Л 0 3 )
~ I V ^ T F .
In o t h e r w o r d s , e v e n in s i m p l e p o t e n t i a l s c a t t e r i n g , q u a n t u m i n t e r f e r e n c e
can o c c u r between c l a s s i c a l t r a j e c t o r i e s which have different impact
p a r a m e t e r s but w h i c h a r e s c a t t e r e d at the s a m e a n g l e в.
A f u l l d i s c u s s i o n of t h e v a r i o u s t y p e s of s c a t t e r i n g p h e n o m e n a in the
f r a m e w o r k of t h e s e m i - c l a s s i c a l t h e o r y i s g i v e n by F o r d and W h e e l e r (1959).
1.9. The rainbow effect
W h e n the d e f l e c t i o n f u n c t i o n 0 ( i ) e x h i b i t s e i t h e r m a x i m a o r m i n i m a
( o r s i n g u l a r i t i e s ) it i s no l o n g e r p o s s i b l e to a p p l y the p r e c e d i n g a n a l y s i s
636 McCARROLL
in a l l c a s e s . A s one a p p r o a c h e s the s c a t t e r i n g a n g l e 0 t c o r r e s p o n d i n g to
one of t h e s e m a x i m a o r m i n i m a , the p o i n t s of s t a t i o n a r y p h a s e c o m e
t o g e t h e r , t h u s i n v a l i d a t i n g t h e u s e of E q . ( 1 . 9 5 ) . In a d d i t i o n г ) ± и ( £ т ) a t a
m a x i m u m o r m i n i m u m i s z e r o . T h e a n a l o g o u s s i t u a t i o n in o p t i c s p r o d u c e s
a r a i n b o w , w h i c h g i v e s r i s e to the n a m e u s e d in s c a t t e r i n g t h e o r y . T h e
s c a t t e r i n g a n g l e 0r i s t e r m e d the r a i n b o w a n g l e .
N e a r the r a i n b o w a n g l e the p h a s e s h i f t 6t and © m a y be e x p a n d e d
using Eq.(l.93)
ó, = ó í r ±iflr(i-ir) (£-£T)3 (1.104)
в{£) = e r + q (£ - £ t ) 2 (1.105)
where
d^©
(1.106)
d£2
Then
nHt) = 2 6 ? r ± e r {£ - £ r ) + f (£ - t T ) 3 ± (£ + i ) f l ± t t / 4 (1.107)
A s s u m i n g t h e r a i n b o w a n g l e t o be the only p o i n t of s t a t i o n a r y p h a s e
2
do \ _ 2тт_ Ut± 1-2/3 Ai (1.108)
dn Jr к2 V sin TT/3
where
Ai(X) = e l ( U X + u3/3) du
h I (1.109)
i s the A i r y i n t e g r a l . F o r x > 0, Ai(x) f a l l s off r a p i d l y w h i l s t f o r x < 0 ,

Ai(x) o s c i l l a t e s . T h u s f o r a n g l e s в < б г , ( d a / d a ) r i s an o s c i l l a t i n g f u n c t i o n .
T h e f i r s t m a x i m u m f o r l a r g e a n g l e s в i s c a l l e d the r a i n b o w a n d t h e
s u c c e s s i v e m a x i m a for s m a l l e r в a r e called s u p e r n u m a r y rainbows.
T h e r a i n b o w m a x i m u m in s c a t t e r i n g e x p e r i m e n t s w a s f i r s t o b s e r v e d
b y B e c k (1961) f o r p o t a s s i u m a t o m s s c a t t e r e d f r o m k r y p t o n . S i n c e t h e n
m a n y o t h e r s y s t e m s h a v e b e e n i n v e s t i g a t e d . F i g u r e s 4 a n d 5 show a
m e a s u r e m e n t of w e l l r e s o l v e d r a i n b o w s c a t t e r i n g f o r t h e c o l l i s i o n
p a r t n e r s N a - H g (Buck and P a u l y , 1971).
T h e r a i n b o w m a x i m a a r e of p a r t i c u l a r i n t e r e s t s i n c e t h e y p r o v i d e a
d i r e c t d e t e r m i n a t i o n of t h e p o s i t i o n and d e p t h of a p o t e n t i a l m i n i m u m .
F o r a f u l l d i s c u s s i o n s e e B e r r y (1966), P a u l y a n d T o e n n i e s (1965).
1.10. T h e h a l o e f f e c t (the g l o r y )
If Q{£) p a s s e s t h r o u g h z e r o o r ±тг, t h e n s i n © ( i ) = 0 w h i l e d © / d i
r e m a i n s f i n i t e . T h e e x p r e s s i o n (1.99) b e c o m e s i n f i n i t e , g i v i n g r i s e t o
I A E A - S M R - 1 2 / 2 6 ,27649
FIG. 4. Differential scattering cross-section for Na-Hg (Buck and Pauly (1971)).
638 McCARROLL
18~]
16
Na-Hg
14
Г-» IP
Ю
s 10
?
? в
s 6
©
© 4
S 10 15 20 25 30 35
в
FIG. 5. Na-Hg rainbow scattering (Buck and Pauly (1971)).
what i s t e r m e d a g l o r y . H o w e v e r , f o r s m a l l a n g l e s e x p r e s s i o n (1.88) is
i n v a l i d . We m u s t u s e i n s t e a d the s m a l l - a n g l e a p p r o x i m a t i o n f o r P ř (cos 6).
F o r e x a m p l e if в is v e r y c l o s e to тг
P c (cos в) ~ (cos в)1 J 0 [ (i +1) б] (1.110)
If the g l o r y o c c u r s at i -ig and 66 is expanded about ig
S, = | (i - £ g ) + j (i-ig)2 +6íg (1.111)
where
d©
b = (1.112)
dí
S u b s t i t u t i n g (1.111) in (1.6) u s i n g (1.110) and the i n t e g r a l a p p r o x i m a t i o n

to the s u m , we then have
Цв) = - ^ exp {i(2ó {g - 7TÍg)} J (2i +1) exp [ | i b ( i - i g ) 2 ] J 0 ( í s i n 0 ) d i

0
(1.113)
T h i s i n t e g r a l m a y be e v a l u a t e d by s u b s t i t u t i n g the i n t e g r a l r e p r e s e n t a t i o n
f o r J 0 and i n v e r t i n g the o r d e r of i n t e g r a t i o n . T h e n we find
% = |f(fl)| 2 - jpr ( * g + è ) 2 v {Jo (ig s i n e ) } 2 (1.114)

IAEA-SMR-12/26, 27 6 3 9
т—1—i—i—i 1
i 1
i 1 I ' i1 i 1 1 1
1—1—r
100 200 300 400 500 600 700 8 0 0 1000 2000 3000 4000
v, [ m / s e c ]
FIG. 6. Measured and calculated total scattering cross-section Q e ff for 4 He- 4 He as a function of the
primary beam velocity (Feltgen et al. (1973)).
When s i n e tends t o z e r o , (1.114) t e n d s to a finite l i m i t in p l a c e of the

u n l i m i t e d c l a s s i c a l v a l u e . At f i n i t e v a l u e s of в, the c r o s s - s e c t i o n
o s c i l l a t e s , an e f f e c t which can be a s c r i b e d to i n t e r f e r e n c e b e t w e e n the
two c o n t r i b u t i o n s f r o m ® < n and © > 7г.
A s i m i l a r r e s u l t is obtained f o r a f o r w a r d g l o r y .
T h e halo e f f e c t c a n e v e n p r o d u c e s t r u c t u r e in the e n e r g y v a r i a t i o n of
the t o t a l c r o s s - s e c t i o n . A d i s c u s s i o n is given by Nikitin and Ovchinnikova
(1972), M a s s e y and B u r h o p (Vol.3^, p.1327). A s t r i k i n g e x a m p l e of the
h a l o e f f e c t in 4 H e - 4 H e c o l l i s i o n s is given by F e l t g e n et a l . (1973) (see F i g . 6 ) .
1.11. Orbiting
An o r b i t i n g s i n g u l a r i t y a r i s e s in the l i m i t when the rainbow angle

t e n d s to infinity. T h e e f f e c t i v e p o t e n t i a l f o r the r a d i a l m o t i o n is
- V • <'•"»>
F o r a m o n o t o n i e r e p u l s i v e p o t e n t i a l V, Veff is a l s o m o n o t o n i e , but if V
i s a t t r a c t i v e the s h a p e of V eff will depend c r i t i c a l l y on I. F o r SL s u f f i -
c i e n t l y l a r g e , Veff w i l l be m o n o t o n i e but f o r l o w e r Í , Veff will in g e n e r a l
have a m a x i m u m and a m i n i m u m . A t y p i c a l c a s e is shown in F i g . 7 .
N e a r a m a x i m u m in a c u r v e s u c h a s I, the c l a s s i c a l r a d i a l v e l o c i t y
b e c o m e s v e r y s m a l l when the e n e r g y E is c l o s e to t h i s m a x i m u m value
of V e f f . T h e p a r t i c l e w i l l then m a k e s e v e r a l r e v o l u t i o n s a r o u n d the
s c a t t e r i n g c e n t r e b e f o r e r e t u r n i n g to i n f i n i t y . Unlike the g l o r y and
r a i n b o w s i n g u l a r i t i e s , a s e m i - c l a s s i c a l a p p r o x i m a t i o n f o r the p h a s e
s h i f t cannot be d e r i v e d when an o r b i t i n g s i n g u l a r i t y i s p r e s e n t . T h u s
we s u p p o s e
Veff(r-i)=El,
640 McCARROLL
FIG. 7. Illustration of the variation of the effective potential for radial motion with г for different
values of the angular momentum, which increases upwards (Mott and Massey (1965) p. 106).
As the a n g u l a r m o m e n t u m d e c r e a s e s below s o m e value of SL > SL\ the

c l a s s i c a l t u r n i n g point m o v e s g r a d u a l l y in until when SL = SL i the t u r n i n g
point o c c u r s at r j . A f u r t h e r d e c r e a s e of SL will c a u s e the t u r n i n g point
t o m a k e a s u d d e n j u m p i n w a r d s s i n c e Veff is now l e s s than E j . T h i s
p r o d u c e s a d i s c o n t i n u i t y in the s e m i - c l a s s i c a l p h a s e s h i f t . T o r e m o v e
s u c h an u n p h y s i c a l b e h a v i o u r , f u l l a c c o u n t m u s t be t a k e n of q u a n t u m -
m e c h a n i c a l t u n n e l l i n g t h r o u g h the p o t e n t i a l b a r r i e r f o r l a r g e SL.
A f u r t h e r i m p o r t a n t i n f l u e n c e of the c l a s s i c a l l y i n a c c e s s i b l e r e g i o n
a r i s e s f r o m the p r e s e n c e of v i r t u a l e n e r g y l e v e l s as i l l u s t r a t e d in F i g . 8 .
Let us c o n s i d e r the v a r i a t i o n of Veff with r at a fixed value of i f o r
which an i n n e r a t t r a c t i v e w e l l e x i s t s . If t h i s w e l l is d e e p and wide enough
t h e r e m a y e x i s t a n u m b e r of e n e r g y l e v e l s within it which f o r E > 0 a r e
not s t a b l e due to l e a k a g e t h r o u g h the b a r r i e r . T h e s e a r e v i r t u a l l e v e l s ,
w h i c h , b e c a u s e of t h e i r f i n i t e l i f e - t i m e , a r e b r o a d e n e d , h a l f - w i d t h Г.
T h e t o t a l c r o s s - s e c t i o n w i l l then exhibit r e s o n a n c e e f f e c t s o v e r an e n e r g y
r a n g e of o r d e r Г at an e n e r g y c o r r e s p o n d i n g to a v i r t u a l l e v e l . In g e n e r a l
the width Г i s so s m a l l that the e n e r g y r e s o l u t i o n a v a i l a b l e in p r a c t i c e
w i l l be i n s u f f i c i e n t to d e t e c t the e f f e c t . H o w e v e r , if the v i r t u a l l e v e l
o c c u r s n e a r the top of the w a l l , the r e s o n a n c e m a y be o b s e r v e d . T h i s is
i l l u s t r a t e d in F i g . 8 .
IAEA-SMR-12/26, 27 641
FIG. 8. (a) V e ff as a function of r for a given value f of the angular momentum.

(b) Variation of with kinetic energy E of relative motion (Massey (1970) p. 1331).
1. 12. Reduced c r o s s - s e c t i o n s
L e t u s r e t u r n to t h e high e n e r g y l i m i t f o r t h e p h a s e s h i f t (Eq. (1. 83))
(1.116)
w h e r e b, the c l a s s i c a l i m p a c t p a r a m e t e r , is r e l a t e d to £ by
m v b = (£ + 1/2) ft (1.117)
T r a n s f o r m i n g to new v a r i a b l e s , we obtain the r e d u c e d angle r and

the r e d u c e d c r o s s - s e c t i o n p a s f o l l o w s
т = E0
p (т, E) = б s i n 0 ст(0, E) (1.118)
T h e n in t e r m s of t h e s e v a r i a b l e s we m a y w r i t e t h e f u n c t i o n s rj* a s
^ (b, E, в) = ~ s g (b, t) (1.119)

642 McCARROLL
where
s*(b, т) = - 2 J (r2 d r ± 2 b r ± ftv тг/4 (1.120)

b
E q u a t i o n (1.93) which d e f i n e s the c l a s s i c a l s c a t t e r i n g a n g l e a s a function

of i m p a c t p a r a m e t e r b e c o m e s
oO
Tâ , _ 2h Эб й г V(r)r . г b dV
т = Е0 = ± 2 Е — = ± E —r- = ± T~r / . о ,2,1/2 d r = ± / 7-3—, — dr
dl m v ЭЬ ЭЬ J (r - b ) ' J (r — b ) dr
b (1.121)
(0 = ± 0 )
T h i s f o r m u l a c o i n c i d e s with t h e c l a s s i c a l f o r m u l a f o r s c a t t e r i n g at s m a l l
a n g l e s . By i n v e r t i n g (1.121) we find t h e i m p a c t p a r a m e t e r b to be a f u n c t i o n
only of r ( a p a r t f r o m h i g h e r t e r m s in V / E )
b=b(r) ' (1.122)
T h u s an e x p a n s i o n in t e r m s of l / E at a fixed angle can be t r e a t e d in t h e

s a m e way a s an e x p a n s i o n in t e r m s of angle at a fixed e n e r g y .
T h e r e d u c e d c r o s s - s e c t i o n , using Eq. (1.34), m a y be w r i t t e n as
o(T'E) - Ě ъв
S = ï d i r ? =р°(т) + 0 (1 E
/ > <1Л23)
t h u s showing t h a t t h e r e d u c e d c r o s s - s e c t i o n is a f u n c t i o n of only one v a r i a b l e

T = E0 in t h e l i m i t of s m a l l a n g l e s o r l a r g e e n e r g i e s .
E x p e r i m e n t a l data o b t a i n e d at d i f f e r e n t e n e r g i e s can then be fitted in
t e r m s of the r e d u c e d p a r a m e t e r s p and т to a s i n g l e c u r v e p (т) o r to a f a m i l y
of c u r v e s h a v i n g a c o m m o n envelope. T h i s i n c r e a s e s the a c c u r a c y and
r e l i a b i l i t y of the e x p e r i m e n t a l р 0 (т), which can b e u s e d to s o l v e the i n v e r s e
problem. F o r example, integration yields
b2(r) = J p0(r')dlnr' (1.124)

T
H o w e v e r , t h e f u n c t i o n r0 (b) is d i r e c t l y r e l a t e d to the p o t e n t i a l f r o m which

it can b e shown ( F i r s o v 1953) t h a t
2 T
wi ^
V ( r ) =
f n(b) db , ( 1 Л 2 5 .)
x j < l J - r 3)1/2
r
T h u s t h e p o t e n t i a l V(r) m a y (in p r i n c i p l e ) be o b t a i n e d f r o m e x p e r i m e n t a l
m e a s u r e m e n t s of t h e r e d u c e d c r o s s - s e c t i o n .
A t y p i c a l e x a m p l e is p r o v i d e d by t h e e l a s t i c s c a t t e r i n g d a t a f o r t h e
s y s t e m H e + - N e . F i g u r e 9 shows the r e d u c e d c r o s s - s e c t i o n s f o r e l a s t i c
s c a t t e r i n g , o b t a i n e d at d i f f e r e n t e n e r g i e s and a n g l e s (Smith et al. , 1967).
T h e p a r a m e t e r s of t h e p o t e n t i a l have b e e n r e c o n s t r u c t e d f r o m t h e s e d a t a .
IAEA-SMR-12/26, 27 643
0
6.5 6 5 4 3 2 I .4 .1 .04
log7" (eVxdeg)
FIG. 9. Cross-sections for elastic and quasi-elastic scattering of He + by Ne in terms of the reduced
variables p and r for different energies. Curves 1 and 2 are theoretical curves for different approximations
to the scattering potentials (Smith et al. (1961)).
1.13. Resonance processes
When i n e l a s t i c s c a t t e r i n g o c c u r s , t h e s t r u c t u r e of t h e d i f f e r e n t i a l
s c a t t e r i n g c r o s s - s e c t i o n s is m u c h m o r e c o m p l e x than in o r d i n a r y p o t e n t i a l
s c a t t e r i n g . H o w e v e r , t h e r e is one type of i n e l a s t i c p r o c e s s which is p a r t i -
c u l a r l y s i m p l e — r e s o n a n c e s y m m e t r i c a l p r o c e s s e s such a s c h a r g e t r a n s f e r ,
spin e x c h a n g e , e x c i t a t i o n t r a n s f e r . T h i s a r i s e s f r o m t h e f a c t t h a t t h e
c o l l i s i o n m a y be d e s c r i b e d in t e r m s of s c a t t e r i n g by d i f f e r e n t p o t e n t i a l s
c o r r e s p o n d i n g to d i f f e r e n t (even and odd) e l e c t r o n i c m o l e c u l a r s t a t e s .
(The v e l o c i t y i s t a k e n s u f f i c i e n t l y low f o r the a d i a b a t i c a p p r o x i m a t i o n to
be valid. No t r a n s i t i o n s b e t w e e n s t a t e s of d i f f e r e n t s y m m e t r y a r e t h e n
allowed. ) T h e s y m m e t r i c a l p r o c e s s thus b e c o m e s a v e r y s i m p l e
g e n e r a l i z a t i o n of t h e p o t e n t i a l s c a t t e r i n g p r o b l e m .
T h e m o s t fully s t u d i e d p r o c e s s of t h i s t y p e i s c h a r g e t r a n s f e r ,
e s p e c i a l l y f o r s y s t e m s such as H + -H, H e + - H e , L i + - L i , N e + - N e . F o r
e x a m p l e , t a k i n g the s y s t e m H + - H , t h e c o l l i s i o n i s g o v e r n e d by two p o t e n t i a l s ,
o n e c o r r e s p o n d i n g to t h e ( l s o g ) 2 £ g s t a t e t h e o t h e r to t h e (2pcru ) 2 L U s t a t e
of H 2 . Initially t h e c h a r g e i s l o c a l i z e d on one of the p a r t i c l e s , so that t h e
644 McCARROLL
s t a t e of t h e s y s t e m p r i o r to the c o l l i s i o n is d e s c r i b e d by a l i n e a r c o m b i n a -
tion of t h e g and u s t a t e s . T h e n denoting by f g , f u the s c a t t e r i n g a m p l i t u d e s
f o r t h e p o t e n t i a l s Vg and V u , it i s e a s y to show t h a t t h e d i f f e r e n t i a l c r o s s -
s e c t i o n f o r e l a s t i c s c a t t e r i n g is given by
a e (0,E) = | f g ( 0 , E ) + f u ( 0 , E ) | 2 (1.126)
and t h a t f o r c h a r g e t r a n s f e r by
о с ( в , Е ) = j f g(0, E) - f u ( 9 , E) | 2 (1.127)
If we u s e t h e s e m i - c l a s s i c a l e x p r e s s i o n s f o r the a m p l i t u d e s , we o b t a i n
( a s s u m i n g no i n t e r f e r e n c e f r o m r a i n b o w s c a t t e r i n g )
/ 2 i 6
*e,c= K e 6 ± a f e i e " |2 (1.128)
w h e r e <rg and CTu a r e the c l a s s i c a l e l a s t i c s c a t t e r i n g c r o s s - s e c t i o n s by t h e

p o t e n t i a l s V and Vu
ßg.u =>1g.u (Jí o) - тг/4 (1.129)
with S.0 a point of s t a t i o n a r y p h a s e ( s e e E q . (1.101)).

T h u s t h e t r a j e c t o r i e s c o r r e s p o n d i n g to d i f f e r e n t i m p a c t p a r a m e t e r s
b B , b u f r o m e a c h of t h e two t e r m s c o n t r i b u t e to i n t e r f e r e n c e at t h e g i v e n
1/2 1/2
a n g l e 0. T h e c r o s s - s e c t i o n o s c i l l a t e s b e t w e e n t h e e n v e l o p e s of (crg ±CTu ).
T h i s s e m i - c l a s s i c a l d e s c r i p t i o n a g r e e s w e l l with e x p e r i m e n t ,
e s p e c i a l l y f o r low v a l u e s of т= E 0 . F o r e x a m p l e , in F i g . 10 is given a
c o m p a r i s o n of the t h e o r e t i c a l and e x p e r i m e n t a l c u r v e s of the d i f f e r e n t i a l
e l a s t i c c r o s s - s e c t i o n of H e + - H e at 300 eV.
The e x p r e s s i o n s (1.128) and (1.129) a r e a p p r o p r i a t e when it is a s s u m e d
t h a t it is p o s s i b l e to d i s t i n g u i s h b e t w e e n c h a r g e t r a n s f e r and e l a s t i c
s c a t t e r i n g . In o t h e r w o r d s , n u c l e a r s y m m e t r y is i g n o r e d . In t h i s f o r m
t h e t h e o r y is a p p l i c a b l e to s c a t t e r i n g of d i f f e r e n t i s o t o p e s of the s a m e
e l e m e n t . When i d e n t i c a l a t o m s a r e involved an a d d i t i o n a l s y m m e t r y e n t e r s .
B e c a u s e of t h e i n d i s t i n g u i s h a b i l i t y of t h e a t o m s , it is i m p o s s i b l e to
d i s t i n g u i s h b e t w e e n d i r e c t s c a t t e r i n g at 0 and c h a r g e e x c h a n g e at v - 9.
When the n u c l e i a r e b o s o n s t h e total w a v e f u n c t i o n m u s t be e v e n , u n d e r
n u c l e a r i n t e r c h a n g e ; when t h e y a r e f e r m i o n s , it m u s t be odd. F o r 4 H e ,
t h e g e r a d e e l e c t r o n i c s t a t e i s a s s o c i a t e d with a s y m m e t r i c n u c l e a r f u n c t i o n
and t h e u n g e r a d e s t a t e with an a n t i s y m m e t r i c n u c l e a r f u n c t i o n .
T h e n in E q s (1.126), (1.127)
f g (0) - f g (0)+f g (7T-0) (1.130)
f u (6) - f u (0) - f u W - 0 ) . (1.131)
which give r i s e to a d d i t i o n a l i n t e r f e r e n c e p a t t e r n s , m o s t p r o n o u n c e d at
l a r g e a n g l e s n e a r 45° in the l a b o r a t o r y f r a m e . . T h u s in the s c a t t e r i n g of
4
H e + by H e only one s e t of o s c i l l a t i o n s i s o b s e r v e d while f o r 4 H e + _ 4 H e
both t y p e s of i n t e r f e r e n c e p a t t e r n a r e o b s e r v e d . R e c e n t r e s u l t s o n
3
H e + - 3 H e indicate s i m i l a r behaviour (see Fig.11).
IAEA-SMR-12/26, 27 645
б CM — degrees
FIG. 10. Differential cross-sections for charge transfer of 4 H e + with 4 H e (Aberth et al. (1965)).
H o w e v e r , an i n t e r p r e t a t i o n of e x p e r i m e n t s on s y m m e t r i c a l r e s o n a n c e
c h a r g e t r a n s f e r on t h e b a s i s of a t w o - s t a t e a p p r o x i m a t i o n d o e s not
c o m p l e t e l y explain the o b s e r v e d p h e n o m e n a . F o r e x a m p l e , at l a r g e a n g l e s
in H e + - H e c o l l i s i o n (around 15° in the c e n t r e of m a s s s y s t e m , 300 eV) t h e
t h e o r e t i c a l l y p r e d i c t e d o s c i l l a t i o n s b e c o m e d e p h a s e d with e x p e r i m e n t .
T h i s cannot b e e x p l a i n e d by i n a c c u r a t e p o t e n t i a l c u r v e s . A s i m i l a r
p h e n o m e n o n o c c u r s i n l f ^ - H c o l l i s i o n s . To explain t h i s and o t h e r e f f e c t s ,
it i s n e c e s s a r y to t a k e account of i n e l a s t i c t r a n s i t i o n s , which, as we s h a l l
s e e l a t e r , h a v e an i m p o r t a n t i n f l u e n c e at l a r g e a n g l e s of s c a t t e r i n g .
6 4 6 McCARROLL
(keVxdeg)
FIG. 11. Oscillatory parts of the reduced cross-section for elastic scattering as a function of the reduced
angle т. 4 H e + - 4 H e (solid line); 3 H e + - 3 H e (dashed line). The relative velocity is the same in
both cases. The oscillations are in antiphase. Curves A, B, D, E are e x p e r i m e n t a l curves for different
energies. Curve С is a t h e o r e t i c a l curve for the s a m e energy as В (Dhuicq et al. (1973)).
2. INELASTIC COLLISIONS
2.1. General theory
Let us c o n s i d e r t h e c o l l i s i o n of two a t o m s A and P . In g e n e r a l t h r e e

t y p e s of r e a c t i o n m a y o c c u r :
(a) e l a s t i c s c a t t e r i n g
A+P ^ A +P (2.1)
T h e a t o m s a r e s i m p l y s c a t t e r e d without any change in t h e i r i n t e r n a l

structure.
(b) i n e l a s t i c s c a t t e r i n g
A+P A* + P * (2.2)
IAEA-SMR-12/26, 27 647
One o r both a t o m s u n d e r g o a change of i n t e r n a l s t r u c t u r e in t h e s c a t t e r i n g

process.
(c) r e a r r a n g e m e n t (or exchange) c o l l i s i o n s
A + P -» B + Q (2.3)
T h e a t o m s A and P e x c h a n g e a c e r t a i n n u m b e r of e l e c t r o n s in the c o l l i s i o n .
A w e l l - k n o w n e x a m p l e is t h a t of c h a r g e e x c h a n g e in i o n - a t o m c o l l i s i o n s .
T h u s in e l a s t i c s c a t t e r i n g , t h e s y s t e m r e m a i n s in the e n t r y channel;
w h e r e a s f o r i n e l a s t i c and r e a r r a n g e m e n t c o l l i s i o n s the exit channel d i f f e r s
f r o m the e n t r y channel.
L e t us denote the p o s s i b l e r e a c t i o n c h a n n e l s by a, ß, . . . For example,
if t h e channel y r e p r e s e n t s two p a r t i c l e s C, T w h o s e c e n t r e s of m a s s a r e
l o c a t e d r e s p e c t i v e l y at R c and R T , it is u s e f u l to i n t r o d u c e t h e v e c t o r
^ MCMT
R y = R c - R f , the r e d u c e d m a s s M y = + and t h e r e l a t i v e m o m e n t u m
^ 2
p y . T h e k i n e t i c e n e r g y a s s o c i a t e d with channel y i s p y / 2 M y .
T h e wave f u n c t i o n d e s c r i b i n g t h e i n t e r n a l s t a t e of t h e p a r t i c l e s in
t h i s c h a n n e l , i s then t h e p r o d u c t of t h e wave function фс and ф? of t h e
p a r t i c l e s С and T. Let h c and h T be the H a m i l t o n i a n s of t h e s e p a r t i c l e s
= е
У с Л Ьтфт=етфт (2.4)
е = е + е
Фу =фсфт у С Т (2-5)
The t o t a l i n t e r n a l e n e r g y of t h e c h a n n e l у is e y .
Let Vy be the i n t e r a c t i o n b e t w e e n t h e p a r t i c l e s С and T . (It m u s t be
a s s u m e d in t h e s u b s e q u e n t a n a l y s i s t h a t V t e n d s to z e r o in t h e l i m i t
R y -*oo m o r e r a p i d l y than l / R y ) .
T h e H a m i l t o n i a n of t h e s y s t e m m a y then be w r i t t e n a s
H = Hy+Vy (2.6)
where
H y = h c + hT + py/2My (2.7)
Let us denote the e n t r y channel ( A + P ) by a . In o r d e r to fix t h e i n i t i a l

c o n d i t i o n s of t h e c o l l i s i o n , t h e r e l a t i v e m o m e n t u m ftka of t h e p a r t i c l e s
in t h e i r i n i t i a l s t a t e m u s t be given. T h e s e t of i n i t i a l c o n d i t i o n s (a, k a )
will t h e n be d e s i g n a t e d by a. We h a v e
E = e +ft2
„ ka/2Ma (2.8)
L e t u s now c o n s i d e r t h e r e a c t i o n
A+P - B+Q
with t h e exit channel (B + Q) denoted by ß. T h e p a r t i c l e s in t h i s channel

l e a v e with r e l a t i v e m o m e n t u m of m a g n i t u d e h k b given by
E = e„ + h 2 k ? / 2 M „ (2.9)
648 McCARROLL
F o r c h a n n e l ß to be open, it is of c o u r s e n e c e s s a r y that (E - e ß ) be p o s i t i v e .
To each s e t of i n i t i a l conditions, we m a y a s s o c i a t e a plane wave
Фа = ф а exp (ik a • R a ) (2.10)
and two s t a t i o n a r y w a v e s >ř a and "Фа, which a r e s o l u t i o n s of t h e S c h r ö d i n g e r

e q u a t i o n with e n e r g y E. The function Sřa h a s an a s y m p t o t i c b e h a v i o u r in t h e
e n t r y c h a n n e l of t h e f o r m ( e x p (ik a • R „ ) + o u t g o i n g wave) and in all o t h e r
c h a n n e l s an a s y m p t o t i c b e h a v i o u r of p u r e l y outgoing w a v e s . T h e function
f a i s defined in an a n a l o g o u s way with ingoing w a v e s .
Thus
Н
аФа=ЕФа (2.11)
.± i
Hi, =£ia (2.12)
exp(ika - R J + f a a ( 4 < > i r ex

P(±ikccRa> (2.13)
S V ^ V R exp(±ikcRy) (2.14)
T h e e x i s t e n c e of such s o l u t i o n s i s a s s u m e d (cf. Newton 1966) without

further discussion.
T h e c r o s s - s e c t i o n s a r e d i r e c t l y r e l a t e d to the a s y m p t o t i c f o r m of t h e
Ф а . T h u s t h e d i f f e r e n t i a l s c a t t e r i n g c r o s s - s e c t i o n f o r the s c a t t e r i n g of В
in t h e d i r e c t i o n fib i s given by
der.
(2.15)
díl.
w h e r e v a = f i k a / M a , v b = ftkb/Mß .
T h e t r a n s i t i o n m a t r i x i s defined a s
. b = = - ^ f > b ; (2.16)
T h e t r a n s i t i o n m a t r i x m a y a l s o be obtained f r o m t h e a s y m p t o t i c f o r m of the
s o l u t i o n Ф а . It m a y be e a s i l y shown t h a t
f
aß(nb)"ivr f
ba(-ncJ (2.17)
M
and c o n s e q u e n t l y t h a t
<b|T|a>- f
b"H(-"a> (2.18)
M
T h e t r a n s i t i o n m a t r i x m a y be e x p r e s s e d in t h e following i n t e g r a l r e p r e s e n t a -
t i o n s (cf. Newton 1966).
IAEA-SMR-12/26, 27 649
 = <Ф Ь |VB | < > (2.19)
= <*blVc<K> < 2 - 2 °)
T h e above m e n t i o n e d p r o p e r t i e s a r e t r u e , w h a t e v e r t h e c o l l i s i o n . F o r
e l a s t i c s c a t t e r i n g a = ß, i n e l a s t i c s c a t t e r i n g af ß, Va = V g , r e a r r a n g e m e n t
c o l l i s i o n s Va f' V. D.
2.2. Eikonal approximation
T h e m e t h o d s d e v e l o p e d in s e c t i o n 4 m a y be e x t e n d e d to o b t a i n an e i k o n a l
wave f u n c t i o n f o r i n e l a s t i c s c a t t e r i n g . T h i s e i k o n a l wave function m a y
t h e n be s u b s e q u e n t l y s u b s t i t u t e d in E q s (2.19) o r (2.20) to o b t a i n t h e r e q u i r e d
scattering amplitude.
In t h e c o u r s e of t h i s p a p e r , we will l i m i t o u r d i s c u s s i o n to d i r e c t
i n e l a s t i c s c a t t e r i n g . T h e e x t e n s i o n to r e a r r a n g e m e n t c o l l i s i o n s is s t r a i g h t -
f o r w a r d but t h e a n a l y s i s b e c o m e s c o m p l e x . T h u s we c o n s i d e r a c o l l i s i o n
of t h e type
A + P ->• A* + P *
w h e r e we m a y s e t
мй = ме= м
Ř a = Rß
L e t us now c h o o s e t h e a x i s a s in F i g . 12: t h e Z - a x i s is t a k e n to be in
t h e d i r e c t i o n of t h e i n i t i a l wave v e c t o r k a , t h e X - a x i s is in t h e p l a n e c o n t a i n -
ing k a and k b . T h e c o - o r d i n a t e s of R a a r e then (X, Y, Z). T h e n t h e
s c a t t e r i n g a m p l i t u d e m a y be w r i t t e n a s
faß М О <2-21>
w h e r e Фь = exp (ikb • Ra)<í>c< •

We now m a k e u s e of t h e fact that the r e d u c e d m a s s /л is m u c h g r e a t e r
t h a n t h e m a s s of an e l e c t r o n . We t h e n expand Ф а in p o w e r s of (1/a0
Ф; = e x p ( i k - R H ) ф Г ^ Ф ^ Ч . . . ] (2.22:
w h e r e к is a v e c t o r in t h e d i r e c t i o n of k a and with m o d u l u s k = s/(kТ+2цё~) =

+ 2 f j e 3 ) . T h i s e x p a n s i o n is an o b v i o u s e x t r a p o l a t i o n of t h e e i k o n a l
a p p r o x i m a t i o n to t h e i n e l a s t i c c a s e . Substitution of (2.22) in t h e S c h r ö d i n g e r
equation y i e l d s
(0) ^ 1 (l)
~ V-S + H - E exp (i/uvZ) Ф +— Ф = 0 (2.23)
2ц r a et
w h e r e H eC = h A + h P + V a and k= ;uv. (2.24)

65 О McCARROLL
FIG. 12. Co-ordinate system.
Setting E = /JV 2 /2 and r e g r o u p i n g the t e r m s , we obtain
U- v 4 (a0 ) + 1
v - ^ - a i v ^ « « X У 2 Ф< 0) + 2 i v ^ *<» - v 1 * 1 »
2 2 2/u
+H а a (2.25)
ц
E q u a t i n g c o e f f i c i e n t s of fi, t h e f i r s t n o n - t r i v i a l equation i s
(0)
ЭФ
= He{ , *a( 0 ) (2.26)
3Z
We m a y then c o n s i d e r (2.26) a s t h e e i k o n a l equation and Ф^0' a s t h e e i k o n a l

wave f u n c t i o n . T h e S c h r ö d i n g e r equation r e d u c e s to a f i r s t - o r d e r equation
in the l i m i t of l a r g e ц. T h e i n i t i a l conditions r e q u i r e d to solve Eq. (2.26) a r e
(0)
Ф exp [i (k a - к) • R ] Ф (2.27)
A Z-
Since t h e d i f f e r e n t i a l e q u a t i o n (2.26) d e p e n d s only p a r a m e t r i c a l l y o n X, Y,

we m a y c o n s i d e r r e c t i l i n e a r t r a j e c t o r i e s and s e t t i n g Z = v r , t r a n s f o r m
Eq.(2.26) to one f o r m a l l y a n a l o g o u s to a t i m e - d e p e n d e n t e q u a t i o n
л -у (0)
(2.28)
Эт eí а
Writing
R =b+ VT (2.29)
w h e r e b= (X, Y, 0), t h e m o d u l u s of b m a y be identified a s t h e i m p a c t

parameter.
IAEA-SMR-12/26, 27 651
The corresponding expression for the s c a t t e r i n g amplitude then b e c o m e s
f ф
ae^ - - f j < < ь Iv ex
P(ik • IФГ >
= d R a e x p [ i ( k - k b ) - R a ] <Ф В | у | ф < 0 ) > (2.30)

9
where the Dirac b r a c k e t s denote integration over the electronic co-ordinates.

L e t f j b e a v e c t o r d i r e c t e d a l o n g t h e X - a x i s a n d of m a g n i t u d e e q u a l to t h e
p r o j e c t i o n of k b o n t h e a x i s
rj = i k f e s i n 0 (2.31)
Then
(k - k b ) • R „ = (k - k b c o s © ) Z - řf. b
~ (к- kb) Z - Я-b (2.32)
and ri • b = r) b c o s tp.
S i n c e the d i f f e r e n t i a l e q u a t i o n (2.26) d o e s not c o n t a i n <p, t h e a z i m u t h a l
v a r i a t i o n of will u n d e r g o no m o d i f i c a t i o n with t h e t i m e т . T h u s
w i l l h a v e the a z i m u t h a l d e p e n d e n c e of ф a . S i n c e V i s of a x i a l s y m m e t r y ,
t h e m a t r i x e l e m e n t of (2.30) w i l l d e p e n d on = e" 1 " 1 * < ф е | у | ф й > м (2.33)
w h e r e <( ф 0 | V | ф a i s i n d e p e n d e n t of (p.
T h e n we m a y w r i t e
2тт
it f i(k-kb)Z / -imu) / -iubcoso) , , (0)
0 ) = à Z e d(
W " í í - l I f>e ,/dbbe <Фа|у|ф, >M (2.34)
о 0
F o r ц l a r g e , we m a y s e t
k _ k b = £ÉL + 0 ( 1 / м )
yielding
•0 2ir «
á Z e i £ ß Z / V
W ® ) - - t I /d^' e
" i m
" / d b b e
" i , l b C 0 S " < Vel V K 0 )
>M (2.35)
- « 0 0
In t h e c a s e w h e r e the a t o m s f o l l o w a r e c t i l i n e a r t r a j e c t o r y and w h e r e
т = Z / v i s t h e t i m e , the c l a s s i c a l t r a n s i t i o n a m p l i t u d e b a g(b) i s given b y
b a ß ( b ) = l i m < ф в е " 1 е в Т |ф ( а 0) > (2.36)

6 5 2 McCARROLL
(0)
U s i n g E q . (2.26) f o r it i s s t r a i g h t f o r w a r d to show t h a t
i / i€oZ/v . I I (0).
baß(b) = - - J d Z e < 4 e M * a '>+0aß (2.37)
We m a y t h u s e x p r e s s t h e s c a t t e r i n g a m p l i t u d e a s an i n t e g r a l of t h e
c l a s s i c a l transition amplitudes over all impact p a r a m e t e r s
. . ijUV / -im<f> / -ii)bcos</> .

f = Ç e
aß 2 J J lbaß-6aßJ
0 0
= i m + 1 ßV J db b [ b a s - 6 a ß ] J m (nb) (2.38)
о
T h e t o t a l c r o s s - s e c t i o n i s given by
Qae = 2тг J ^ |faS(©)|2 d cos© (2.39)

о
where
гk b = 1 + 0
( \- ß
T h e n f r o m (2.38) and (2.39)

TT *>
Qaß = 2тг / d c o s © IJUV/db b J m (rjb) [b a ß - 6 a ß ] f (2.40)

о 0
T h e m a i n c o n t r i b u t i o n to Q a ß c o m e s f r o m s c a t t e r i n g in t h e f o r w a r d d i r e c t i o n ,
so t h a t we m a y put
n dr] ^ u v s i n © d©
Consequently
Qaß = 2тг J á n n I / d b b J m (rjb) [b a ß - 6 a ß ] | 2 (2.41)

о о
R e p l a c i n g the u p p e r l i m i t of i n t e g r a t i o n b y да and a p p l y i n g the t h e o r y of

Hankel t r a n s f o r m s
f ( r ) = / d r ! J m (rn) И / d b J m (nb) f ( b ) ' b (2.42)

о 0
lAEA-SMR-12/40, 41 653
we obtain
2
Q aß ~ 2?r / d b b lb a g - 6 a ß ] (2.43)
о
E q u a t i o n (2.43) i s of c o u r s e the s t a n d a r d e x p r e s s i o n obtained by the i m p a c t
p a r a m e t e r m e t h o d ( B a t e s , 1962). H o w e v e r , the d e r i v a t i o n we have given
s h o w s not only the n a t u r e of t h e a p p r o x i m a t i o n s involved but a l s o how
f o r m u l a (2.21) m a y be u s e d to c a l c u l a t e the d i f f e r e n t i a l s c a t t e r i n g c r o s s -
s e c t i o n . It should be noted that, s i n c e in g e n e r a l beg i s a c o m p l e x f u n c t i o n ,
i n t e g r a t i o n o v e r b in (2.38) will give r i s e to a n a l o g o u s i n t e r f e r e n c e e f f e c t s
a s in the c a s e of e l a s t i c s c a t t e r i n g .
The above d e r i v a t i o n , which i s valid only f o r d i r e c t e x c i t a t i o n p r o c e s s e s ,
m a y be e a s i l y e x t e n d e d to t r e a t e x c h a n g e p r o c e s s e s . The d e t a i l e d a n a l y s i s
m u s t be p e r f o r m e d with s o m e c a r e but t h e r e a r e no f u n d a m e n t a l d i f f i c u l t i e s
( M c C a r r o l l and Salin, 1968).
The p r e c e d i n g e i k o n a l f o r m u l a t i o n of i n e l a s t i c t r a n s i t i o n s h a s p r o v e d
e x t r e m e l y u s e f u l f o r quantitative c a l c u l a t i o n s both of t o t a l and d i f f e r e n t i a l
s c a t t e r i n g c r o s s - s e c t i o n s . A s we s h a l l s e e l a t e r the m a i n m o t i v a t i o n f o r
s u c h c a l c u l a t i o n s a r i s e s f r o m the p r o b l e m of i n t e r p r e t a t i o n in c o l l i s i o n
s p e c t r o s c o p y . F o r t u n a t e l y at the e n e r g i e s i n v e s t i g a t e d (500 eV - 5 keV),
s c a t t e r i n g t a k e s p l a c e at s m a l l a n g l e s , w h e r e the e i k o n a l m e t h o d i s e x p e c t e d
to be v a l i d . H o w e v e r , the l i m i t s of v a l i d i t y of Eq. (2.38) a r e not well d e t e r -
m i n e d at the p r e s e n t day. In p r i n c i p l e , it is p o s s i b l e to i m p r o v e the a c c u r a c y
of the m e t h o d by t a k i n g a c c o u n t of Ф' 1 ' in (2.22) but in p r a c t i c e t h i s would
p r o v e d i f f i c u l t . Indeed t h e r e i s one f u n d a m e n t a l d i f f e r e n c e in the a p p l i c a t i o n
of the e i k o n a l m e t h o d to i n e l a s t i c c o l l i s i o n a s d i s t i n c t f r o m p o t e n t i a l s c a t -
t e r i n g . F o r p o t e n t i a l s c a t t e r i n g , a c l a s s i c a l t r a j e c t o r y can be r i g o r o u s l y
d e f i n e d (Eq. (1.38)). H o w e v e r , in the i n e l a s t i c c a s e a r i g o r o u s definition i s
i m p o s s i b l e (of c o u r s e in s p e c i a l c i r c u m s t a n c e s , t h e r e m a y be s o m e a v e r a g e
t r a j e c t o r y which r e p r e s e n t s t h e c o l l i s i o n ) . It i s t h e r e f o r e c o n s i s t e n t to adopt
Eq. (2.22) which to z e r o - o r d e r c o r r e s p o n d s to s t r a i g h t - l i n e t r a j e c t o r i e s .
By a n a l o g y with s e c t i o n 1.6. an a l t e r n a t i v e a p p r o a c h is to expand the
w a v e - f u n c t i o n in p a r t i a l w a v e s . The r e s u l t i n g r a d i a l d i f f e r e n t i a l e q u a t i o n s
m a y then be solved by the J . W. К. B. m e t h o d . H o w e v e r , the s i t u a t i o n i s
m o r e c o m p l i c a t e d then f o r p o t e n t i a l s c a t t e r i n g . P h y s i c a l l y it i s l o g i c a l to
u s e a b a s i s s e t of m o l e c u l a r wave f u n c t i o n s . H o w e v e r , it i s not a l w a y s
c o n v e n i e n t to e x p r e s s the a s y m p t o t i c conditions of the c o l l i s i o n p r o b l e m in
a m o l e c u l a r b a s i s s e t , in p a r t i c u l a r when account m u s t be t a k e n of s p i n -
o r b i t i n t e r a c t i o n . B e s i d e s , t h e f o r m of s e m i - c l a s s i c a l a p p r o x i m a t i o n
d e p e n d s on t h e b a s i s set u s e d . Although the c o m p l e t e s e m i - c l a s s i c a l
m e t h o d i s s u p e r i o r in p r i n c i p l e to t h e e i k o n a l m e t h o d , the m e t h o d of a p p l i c a -
tion in any given c a s e i s not a l w a y s evident. A d e s c r i p t i o n of t h i s m e t h o d
i s given by B e r s o n (1968).
2.3. E i k o n a l equation — a t o m i c and m o l e c u l a r r e p r e s e n t a t i o n s
The b a s i c p r o b l e m in the e i k o n a l a p p r o x i m a t i o n i s the solution of the

t i m e - d e p e n d e n t S c h r ö d i n g e r equation
(2.44)
654 McCARROLL
w h e r e H e í d e p e n d s on t t h r o u g h the r e l a t i o n s h i p
r a = b + vt; b•v =0
The m o s t c o m m o n l y adopted p r o c e d u r e i s to expand Ф ^ in the f o r m
(0) - V - -
\Pa ( r , t ) = I a n (t) x n ( r , R ) (2.45)
n
w h e r e x n ( r . R ) r e p r e s e n t s a c o m p l e t e b a s i s s e t , whose a s y m p t o t i c f o r m s
d e f i n e the p o s s i b l e s c a t t e r i n g c h a n n e l s . T h e c o n s t r u c t i o n of s u i t a b l e s e t s
of f u n c t i o n s i s guided by p h y s i c a l c o n s i d e r a t i o n s , the u l t i m a t e a i m b e i n g
to p r o v i d e an a c c u r a t e r e p r e s e n t a t i o n of t h e wave f u n c t i o n when the s e t
X.N i s t r u n c a t e d to a few t e r m s . Only t h e n do the r e s u l t i n g e q u a t i o n s b e c o m e
of m a n a g e a b l e s i z e f o r c o m p u t a t i o n .
At v e r y low e n e r g i e s , w h e r e n e a r l y a d i a b a t i c conditions a r e a p p l i c a b l e ,
the m o l e c u l a r wave f u n c t i o n s defined by
H e S ( ? , R ) фп ( r , R ) = e n ( R ) фп(r,R) (2.46)
f o r m t h e b a s i s of a c o n v e n i e n t e x p a n s i o n . The f u n c t i o n s x n m a y t h e n be
c h o s e n to be t h o s e c o m b i n a t i o n s of the m o l e c u l a r wave f u n c t i o n s фп which
s a t i s f y the b o u n d a r y c o n d i t i o n s . T h i s e x p a n s i o n i s s o m e t i m e s c a l l e d the
perturbed stationary-state method.
When the r e l a t i v e v e l o c i t y of the n u c l e i b e c o m e s c o m p a r a b l e with the
e l e c t r o n i c v e l o c i t y , t h e wave function d o e s not a d j u s t a d i a b a t i c a l l y to the
n u c l e a r m o t i o n and the m o l e c u l a r r e p r e s e n t a t i o n will be i n a d e q u a t e . U n d e r
t h e s e conditions the e l e c t r o n s a r e a s s o c i a t e d f o r m o s t of the t i m e with
one o r o t h e r of the n u c l e i . It i s then m o r e r e a s o n a b l e to u s e an e x p a n s i o n
b a s e d on a t o m i c wave f u n c t i o n s .
In t a k i n g the d e r i v a t i v e of x n with r e s p e c t to t, g r e a t c a r e m u s t be
e x e r c i s e d in s p e c i f y i n g the a x i s of q u a n t i z a t i o n . In g e n e r a l m o l e c u l a r
wave f u n c t i o n s a r e s p e c i f i e d by t a k i n g the i n t e r n u c l e a r a x i s a s the a x i s
of q u a n t i z a t i o n . D u r i n g the c o l l i s i o n t h e i n t e r n u c l e a r a x i s r o t a t e s so that
the q u a n t i z a t i o n i s with r e s p e c t to a r o t a t i n g c o - o r d i n a t e s y s t e m . H o w e v e r ,
the d e r i v a t i v e Э / a t m u s t be t a k e n with r fixed in s p a c e . Then if ft m a k e s
an angle a with the Z - a x i s
sin a = ^ c o s or = | r (2.47)
Ja К
The p l a n e of r o t a t i o n i s c h o s e n to be the (x, z) p l a n e . If ( x \ y ' , z ' ) a r e the

c o m p o n e n t s of r with r e s p e c t to the r o t a t i n g a x e s with the z ' a x i s along R
and (x, y, z) a r e the c o - o r d i n a t e s of r with r e s p e c t to a x e s fixed in s p a c e ,
with z in the d i r e c t i o n of i n c i d e n c e .
then x ' = x c o s a + z sin a
У =У (2.48)
z ' = z c o s a - x sin a
1AEA-SMR-12/40, 41 655
1 Э z R+
The o p e r a t o r 9 / 9 t = —
v
— a p p l i e d to the m o l e c u l a r wave f u n c t i o n x n (x', У', )
y i•e lиd s
9 A DÍŘ
, , , ' ^ I , " (2.49)
where d'/'dZ d e n o t e s d i f f e r e n t i a t i o n with r e s p e c t to x ' , y ' , z ' f i x e d . Since
H - - ! «
we m a y w r i t e
Э !L + i . _ 2 т. Kn
= (2.51)
9Z 9Z h R У'
The m a t r i x e l e m e n t s of Ly> couple s t r o n g l y wave f u n c t i o n s which d i f f e r in

m a g n e t i c q u a n t u m n u m b e r . T h i s coupling r e p r e s e n t s the C o r i o l i s f o r c e ,
a r i s i n g f r o m the r o t a t i o n of t h e c o - o r d i n a t e s y s t e m in which the wave
f u n c t i o n s a r e d e f i n e d . We s h a l l c a l l it r o t a t i o n a l coupling. Coupling due
to the o p e r a t o r Э ' / 9 Z i s c a l l e d r a d i a l coupling.
If a t o m i c wave f u n c t i o n s a r e u s e d , the a x i s of q u a n t i z a t i o n m a y be
e i t h e r t a k e n to be fixed in s p a c e o r to be the r o t a t i n g n u c l e a r a x i s . E i t h e r
c h o i c e i s a d m i s s i b l e p r o v i d e d t h a t the d e r i v a t i v e 9 / 9 Z i s c o n s i s t e n t l y c a l -
c u l a t e d with r c o n s t a n t r e l a t i v e to a fixed a x i s and with f i x e d b.
2.4. E x p a n s i o n in m o l e c u l a r wave f u n c t i o n s
A s m e n t i o n e d in the p r e c e d i n g s e c t i o n s slow c o l l i s i o n s a r e well d e s c r i b e d

by an e x p a n s i o n in t e r m s of m o l e c u l a r f u n c t i o n s i// n (r,R) d e f i n e d a s t h e s o l u -
tion of the e q u a t i o n
[ H e l - en(R)] Фп(r,R) = 0 (2.52)
w h e r e R e n t e r s a s a fixed p a r a m e t e r .
To e x a m i n e t h i s p r o b l e m , it i s u s e f u l to c o n s i d e r f i r s t t h e p r o b l e m of
one a c t i v e e l e c t r o n in the f i e l d of two h e a v y p a r t i c l e s A, B. Then E q . (2.52)
m a y be w r i t t e n a s
1 1 V + V + V + V - e (R) фп( r , R ) = 0. (2.53)

r Ae Be AB n
2m
The i n t e r n u c l e a r p o t e n t i a l VAB i s c o n s t a n t f o r fixed R , so t h a t the t o t a l e n e r g y

e n ( R ) m a y be t a k e n a s the s u m of VAB and an e l e c t r o n i c e n e r g y e n ' (R)
e n ( R ) = VAB + e n . (R) (2.54)

656 McCARROLL
T h e s y s t e m i s s y m m e t r i c a l with r e s p e c t to r o t a t i o n s about t h e i n t e r n u c l e a r
a x i s so t h a t the c o m p o n e n t of the a n g u l a r m o m e n t u m a l o n g t h e i n t e r n u c l e a r
a x i s , X, i s a good q u a n t u m n u m b e r . The e i g e n v a l u e s d e p e n d on | x | r a t h e r
t h a n X s i n c e t h e H a m i l t o n i a n i s i n v a r i a n t u n d e r r e f l e c t i o n s (r -> - r , Pi -> - R ) .
Two a d d i t i o n a l q u a n t u m n u m b e r s a r e r e q u i r e d to s p e c i f y a given s t a t e .
T h e r e a r e two p o s s i b l e w a y s of c h o s i n g t h e m . The f i r s t i s to c o n s i d e r
t h e u n i t e d - a t o m s l i m i t , in which the n u c l e i A and В c o i n c i d e f o r m i n g a
n u c l e u s of c h a r g e ( Z A + Z B ) . In t h i s c a s e , t h e wave f u n c t i o n i s h y d r o g e n i c
and i s s p e c i f i e d by t h e q u a n t u m n u m b e r s (n, S,m) w h e r e m c o i n c i d e s with
X. T h e s t a t e s m a y t h e n be d e s i g n a t e d a s I s a , 2pa, 2pк e t c . , w h e r e a , ж, 6 . . .
s t a n d f o r | x | = 0, 1, 2. . . F o r a s y s t e m with m o r e t h a n one e l e c t r o n , the
c o m p o n e n t of the a n g u l a r m o m e n t u m a l o n g t h e a x i s r e m a i n s a c o n s t a n t of
m o t i o n . The t o t a l c o m p o n e n t of the a n g u l a r m o m e n t u m i s t h e n d e s i g n a t e d
b y E, П , Д . . . f o r E Xj = 0, 1, 2 . . . . T h e n u m b e r s n, i a r e n o t , of c o u r s e ,
good q u a n t u m n u m b e r s s i n c e t h e y do not r e p r e s e n t c o n s t a n t s of m o t i o n as
the i n t e r n u c l e a r distance v a r i e s .
T h e o t h e r way to d e s i g n a t e t h e s t a t e s i s to c o n s i d e r t h e l i m i t of v e r y
l a r g e R , t h e s e p a r a t e d - a t o m s l i m i t . In t h i s c a s e t h e e l e c t r o n m u s t b e c o m e
a t t a c h e d e i t h e r to one n u c l e u s o r the o t h e r . It i s t h e n p o s s i b l e to c o n s t r u c t
a c o r r e l a t i o n d i a g r a m which l i n k s the s t a t e s d e f i n e d in t h e u n i t e d - a t o m s
l i m i t to t h o s e d e f i n e d in the s e p a r a t e d - a t o m s l i m i t .
When t h e n u c l e i h a v e t h e s a m e c h a r g e , the s y s t e m i s i n v a r i a n t u n d e r
r e f l e c t i o n about t h e m i d - p o i n t of the i n t e r n u c l e a r l i n e . The e l e c t r o n i c
w a v e f u n c t i o n s f a l l into two s y m m e t r y c l a s s e s l a b e l l e d g ( g e r a d e ) and u
( u n g e r a d e ) in which t h e wave f u n c t i o n s a r e r e s p e c t i v e l y s y m m e t r i c and
a n t i s y m m e t r i c u n d e r r e f l e c t i o n in the p l a n e p e r p e n d i c u l a r t o (and b i s e c t i n g )
the i n t e r n u c l e a r axis.
T h e p r o p e r t i e s of o n e - e l e c t r o n wave f u n c t i o n s d e p e n d on t h e s e p a r a b i l i t y
of t h e S c h r ö d i n g e r e q u a t i o n in e l l i p t i c c o - o r d i n a t e s f o r t h e t w o - c e n t r e p r o b -
l e m with an e l e c t r o n in the C o u l o m b f i e l d of two n u c l e i . T h e s o l u t i o n s a r e
of t h e f o r m
! / / ( ? , R ) = F ( ? ) G(RJ) E L M * (2.55)
w h e r e Ç = ( r a + r b ) / R , r) = (r a - r b ) / R , <p i s t h e a z i m u t h a l a n g l e m e a s u r e d
f r o m t h e i n t e r n u c l e a r a x i s , r a and r b a r e t h e d i s t a n c e s of t h e e l e c t r o n f r o m
e a c h of t h e two n u c l e i , and R i s t h e i n t e r n u c l e a r d i s t a n c e .
M o r s e and S t ü c k e l b e r g (1929) f i r s t s h o w e d how t h r e e q u a n t u m n u m b e r s
a r i s e in t h e t w o - c e n t r e p r o b l e m : n ^ , n 2 , n 3 a r e t h e n u m b e r s of n o d a l s u r -
f a c e s c o r r e s p o n d i n g to r o o t s of t h e f u n c t i o n (2.55) w h e r e n j = n 6 , n 2 = n 4 ,
n 3 = n ^ . S i n c e t h e n u m b e r of n o d a l s u r f a c e s i s c o n s e r v e d f o r a l l i n t e r -
n u c l e a r d i s t a n c e s , t h e s e q u a n t u m n u m b e r s a r e good. T h i s p r o p e r t y h a s
b e e n u s e d by M o r s e and S t ü c k e l b e r g , B a t e s and C a r s o n (1956), G e r s h t e i n
and K r i v c h e n k o v (1961) to m a k e t h e c o n n e c t i o n b e t w e e n t h e u n i t e d - a t o m s
and s e p a r a t e d - a t o m s l i m i t s . A f u l l d i s c u s s i o n i s given b y B a r a t and
L i c h t e n (1972).
T h e f i g u r e s 13, 14, 15 show the c o r r e l a t i o n d i a g r a m f o r t h e s y m m e t r i c
H 2 s y s t e m and f o r two t y p i c a l n o n - s y m m e t r i c c a s e s .
Of p a r t i c u l a r i n t e r e s t in t h i s d i a g r a m i s the e l e c t r o n p r o m o t i o n m e c h a -
n i s m of Hund (1927) and M u l l i k e n (1928) in which e l e c t r o n s c a n h a v e a h i g h e r
p r i n c i p a l q u a n t u m n u m b e r in going f r o m s e p a r a t e d a t o m s to u n i t e d a t o m s .
IAEA-SMR-12/26, 27 657
MО LINEAR SER
STARK ATOMS
EFFECT R*CO
(П|,пг,т)
LARGE R
\ \ < L > 3Ö0X
tiz>
4f» ч
3d8 -^flIO 1
5fer ' T I 002 J
4da-
^>011
1 £ > 020'
! ! £ : > юо
3dTT- • 001
2p ж-
010
ta>
000
u / > •
F1G. 13. Correlation diagram for Нг. T h e lineaT Stark e f f e c t upon the order of energy levels is shown
both for s m a l l and large internuclear distances. For simplicity only о molecular orbitals are drawn.
P r o m o t i o n is i m p o r t a n t in a t o m i c c o l l i s i o n s , s i n c e e n e r g y l e v e l s f r o m the
s a m e s h e l l and of c o m p a r a b l e e n e r g y b e f o r e c o l l i s i o n can be widely s e p a r a t e d
a f t e r p r o m o t i o n . Since, in addition, t h e r e a r e m a n y c r o s s i n g s of e n e r g y
l e v e l s ( p a r t i c u l a r l y at R = 0 o r R = со), t r a n s i t i o n s b e t w e e n m o l e c u l a r o r b i t a l s
can l e a v e a p r o m o t e d e l e c t r o n in a h i g h e r l e v e l a f t e r the c o l l i s i o n . P r o m o -
tion m a y then l e a d to a v e r y high e x c i t a t i o n in a c o l l i s i o n .
It m a y a l s o be r e m a r k e d that the l i n e a r S t a r k s h i f t s of the s e p a r a t e d
a t o m s a r e g e n e r a l l y in t h e o p p o s i t e d i r e c t i o n to t h a t of the p r o m o t i o n . F o r
e x a m p l e , the 4fcr i s the m o s t s t r o n g l y p r o m o t e d of the s t a t e s a r i s i n g f r o m
the l e v e l n = 2 in t h e s e p a r a t e d - a t o m s l i m i t . Yet t h i s s t a t e i s the one which
i s s u b j e c t to the s t r o n g e s t downw.ard S t a r k s h i f t . T h e s e o p p o s i n g e f f e c t s
c a u s e an i n t e n s i v e s e r i e s of c r o s s i n g s at l a r g e i n t e r n u c l e a r d i s t a n c e s which
a r e r e s p o n s i b l e f o r t h e R o s e n t h a l e f f e c t (1969).
T h e c o r r e l a t i o n d i a g r a m f o r m a n y - e l e c t r o n s y s t e m s can be c o n s t r u c t e d
in an a n a l o g o u s way to t h a t f o r H 2 , except t h a t we m u s t a c c o u n t of t h e ' n o n -
c r o s s i n g r u l e 1 which f o r b i d s c r o s s i n g of p o t e n t i a l e n e r g y c u r v e s f o r two
658 McCARROLL
SMALL M 0 LINEAR SER

R STARK ATOMS
EFFECT R.s
л
LARGE R
5pa 300 \
5dTT 201
6f<r Г2Ю '
•5f8 1102
•ejTT rill
5g* 1003
7h<r /012
•6hi 1120
7lir 021
8k<r 030
4so- — 300 \
4pir — 201
5da" ^f2IO 1
4dft 'Чюг .
5frr ^jlll
4fA -яооз;
>3b
FIG. 14. Correlation diagram for one electron in the field of two nearly equally charged nuclei. Stark
effect is shown at small and large R.
s t a t e s of the s a m e s y m m e t r y . H o w e v e r , in o r d e r to i n v e s t i g a t e p o s s i b l e
i n e l a s t i c t r a n s i t i o n s , we m u s t know w h e r e the e n e r g y c u r v e s of the a c c e s -
s i b l e m o l e c u l a r s t a t e s a r e s u b j e c t to ' p s e u d o - c r o s s i n g s ' with e x c i t e d s t a t e s .
(Of c o u r s e , if the e n e r g y c u r v e s f o r all the m o l e c u l a r s t a t e s could be c a l -
c u l a t e d e x a c t l y , no such p r o b l e m would e x i s t . ) B e s i d e s it t u r n s out that
the a d i a b a t i c m o l e c u l a r s t a t e s a r e not a l w a y s well a d a p t e d to the c o l l i s i o n
p r o b l e m when e x c i t a t i o n o c c u r s .
In m o l e c u l a r s t r u c t u r e t h e o r y , the independent p a r t i c l e m o d e l , in which
e a c h e l e c t r o n i s a s s u m e d to be a s s o c i a t e d with a m o l e c u l a r o r b i t a l , h a s b e e n
u s e d with c o n s i d e r a b l e s u c c e s s . T h u s a given e n e r g y s t a t e m a y be d e s c r i b e d
by a c o n f i g u r a t i o n of o n e - e l e c t r o n m o l e c u l a r o r b i t a l s . T h e c o r r e s p o n d i n g
wave f u n c t i o n s , which a r e m a d e up f r o m a n t i s y m m e t r i z e d p r o d u c t s of o n e -
e l e c t r o n m o l e c u l a r o r b i t a l s , c o r r e s p o n d to what a r e t e r m e d d i a b a t i c m o l e -
c u l a r s t a t e s . In c o n t r a s t to the a d i a b a t i c s t a t e s , t h i s a p p r o a c h y i e l d s e n e r g y
I A E A - S M R - 1 2 / 2 6 , 27 659
UNITED SMALL MО LINEAR SEP

ATOM R STARK ATOMS
R=0 EFFECT R=eo
(П|,п'2,п{) n
LARGE R
z*z0+zb Z„"2Z„
To n = 6
4s<r— 3 0 0
4ртг — 201
.4d8 ~ J I 0 2
4po-^l2IO
4fф - J 0 0 3
4 d i r ' l III
3SO- — 2 0 0
3pir —101
3d8 J002
Зр(гП.|10
3dir—Oil
4»<r — 0 2 0
FIG. 15. C o r r e l a t i o n d i a g r a m for an e l e c t r o n in t h e f i e l d of t w o n u c l e i , w h e r e o n e h a s t w i c e t h e c h a r g e

of t h e o t h e r .
c u r v e s which o f t e n v i o l a t e the n o n - c r o s s i n g r u l e and which m a y e x i s t in t h e

i o n i z a t i o n c o n t i n u u m . The d i a b a t i c c o r r e l a t i o n d i a g r a m m a y then be
c o n s t r u c t e d u s i n g the d i a g r a m s of F i g s 13-15 with c e r t a i n m i n o r m o d i f i c a -
t i o n s . In p a r t i c u l a r the i n c o m p l e t e shielding o r p e n e t r a t i o n of i n n e r s h e l l s
by o u t e r - s h e l l e l e c t r o n s will r e m o v e t h e d e g e n e r a c y of s e p a r a t e d - ( a n d
u n i t e d - ) a t o m s l e v e l s of the s a m e p r i n c i p a l q u a n t u m n u m b e r . T h u s m a n y
of the c r o s s i n g s due to t h e l i n e a r S t a r k e f f e c t f o r the o n e - e l e c t r o n s y s t e m
will d i s a p p e a r ; s e e F i g s 16 and 17.
P e r h a p s the b e s t way to i l l u s t r a t e the s t r i k i n g d i f f e r e n c e s b e t w e e n the
a d i a b a t i c and d i a b a t i c a p p r o a c h i s to c o n s i d e r a s i m p l e e x a m p l e , such a s
He2. The s e p a r a t e d - a t o m s l i m i t in the ground s t a t e c o n s i s t s of H e + ( l s )
+ He ( I s 2 ) , which g i v e s r i s e to two m o l e c u l a r s t a t e s Ej, In the нжхЬех
m o l e c u l a r - o r b i t a l a p p r o a c h t h e X 2 £ u s t a t e h a s the c o n f i g u r a t i o n (lscr g ) 2 (2pa u )
while the X 2 Eg s t a t e h a s t h e c o n f i g u r a t i o n (lso-g) ( 2 p a u ) 2 . Since s i m p l e c a l -
c u l a t i o n s show the ( l s o g ) o r b i t a l to be a t t r a c t i v e and the (2pa u ) o r b i t a l to
be r e p u l s i v e , it is t r i v i a l to e s t a b l i s h the 2EU s t a t e a s the ground s t a t e . The
2
L u s t a t e i s c o r r e l a t e d in the u n i t e d - a t o m s l i m i t to Be + ( l s 2 2 p ) . T h e 2 £ g
s t a t e in the d i a b a t i c a p p r o a c h i s c o r r e l a t e d to B e + ( l s 2 p 2 ), a s t a t e which,
lying in the c o n t i n u u m , is s u b j e c t to a u t o - i o n i z a t i o n . The s e p a r a t e d - a t o m s
l i m i t in an e x c i t e d s t a t e s u c h a s He + (Is) + He ( I s , 2s) will a l s o give r i s e
to an ALg and A £ u s t a t e . In t h i s c a s e th.6 s t a t e will h a v e the c o n f i g u r a -
tion ( l s a o ) 2 (2so"o), all a t t r a c t i v e o r b i t a l s , and will be c o r r e l a t e d to
660 McCARROLL
FIG. 16. Correlation diagram for a symmetric diatomic system with many electrons.
Be + (1S 2 2S). T h u s in a d i a b a t i c a p p r o a c h t h e r e p u l s i v e Eg s t a t e
a r i s i n g f r o m t h e s e p a r a t e d a t o m s in t h e i r g r o u n d s t a t e will c r o s s t h e
a t t r a c t i v e s t a t e s a r i s i n g f r o m t h e s e p a r a t e d - a t o m s in e x c i t e d s t a t e s . On
t h e o t h e r hand in an a d i a b a t i c a p p r o a c h s u c h c r o s s i n g s a r e a v o i d e d ; s e e
a l s o F i g . 18.
2.5. Solution of the e i k o n a l e q u a t i o n
T o i n v e s t i g a t e the a d v a n t a g e s of the d i a b a t i c a p p r o a c h , l e t u s r e t u r n
to the t i m e - d e p e n d e n t S c h r ö d i n g e r e q u a t i o n
H e i - i f t - *<°> = 0 (2.56)
T h e w a v e f u n c t i o n w i l l be e x p a n d e d e i t h e r on an a d i a b a t i c b a s i s фа(r, R) o r
on a d i a b a t i c b a s i s фл{г, R)
a, d
* ( ? , t) = £ a„(t) 0 n a ' d ( ? , R) e x p H • dt (2.57)
n
Hnňd =
< Фп А I Hei | 0 n , d > (2.58)
IAEA-SMR-12/26, 27 661
UNITED
ATOM
FIG. 17. Correlation diagram for many electrons in the field of two slightly different charged nuclei
(Barat and Lichten (1972)).
FIG. 18. Schematic correlation diagram for He + - He to illustrate the diabatic crossing of two 2 £„ states.
662 McCARROLL
S u b s t i t u t i o n of (2.57) in (2.56) y i e l d s
= a- n V n n . ( t ) e x p [ - ^ J " (H n n - H n V ) dt (2.59)
nVn
where
v1 r a, d / . a , d|TT Э I a,d \
nrť = 4 </V | H e ? - i h — j фп: > (2.60)
It is i m p o r t a n t to note t h a t , w h e r e a s the a d i a b a t i c m a t r i x e l e m e n t
<0.?lHe«kn- ) (2.61)
is p u r e l y d i a g o n a l , the c o r r e s p o n d i n g d i a b a t i c m a t r i x e l e m e n t
H d
< < l e i k > (2.62)
m a y be n o n - d i a g o n a l .
T h e t e r m exp [ - i / h J (H nn - H n v ) dt] o s c i l l a t e s r a p i d l y e x c e p t when
H n n d i f f e r s little f r o m H n ' n ' . I n e l a s t i c t r a n s i t i o n s c a n thus o c c u r with
high p r o b a b i l i t y only in the v i c i n i t y of d i a b a t i c c r o s s i n g s o r avoided
c r o s s i n g s . Of c o u r s e , f o r an i n e l a s t i c t r a n s i t i o n to take p l a c e it is not
s u f f i c i e n t to have a c r o s s i n g ; the t r a n s i t i o n p r o b a b i l i t y d e p e n d s a l s o on
t h e b e h a v i o u r of V n n ' .
Using Eq.(2.51) the m a t r i x e l e m e n t Vnn> m a y be w r i t t e n a s
Vnn' = |Hel + | â Ly. - ih 7 - VR^na.'d> (2.63)
In the d i a b a t i c f r a m e w o r k , the c o n t r i b u t i o n s to the m a t r i x e l e m e n t a r e

s u b j e c t to the following s e l e c t i o n r u l e s ( L i c h t e n , 1967):
Ly' ( r o t a t i o n a l coupling): Д т , = ± 1 , p a r i t y c o n s e r v e d , one o r b i t a l c h a n g e
v-VR ( r a d i a l coupling): Am q = 0, p a r i t y c o n s e r v e d , one o r b i t a l change
Hei ( c o n f i g u r a t i o n i n t e r a c t i o n ) : no s p e c i a l s e l e c t i o n r u l e , p a r i t y not
necessarily conserved.
Since d i a b a t i c s t a t e s of the s a m e s y m m e t r y which c r o s s d i f f e r in m o s t

c a s e s by two o r b i t a l s , the i n f l u e n c e of r a d i a l coupling is u s u a l l y w e a k .
F o r e x a m p l e in HeJ the [(1 SCTg)(2 рсти ) 2 ] 2 E g s t a t e d i f f e r s by two o r b i t a l s
f r o m the [(1 s a g ) 2 2 s a g ] 2 Eg s t a t e . In t h i s c a s e the m a i n c o n t r i b u t i o n to
(2.63) a r i s e s f r o m H e t .
In the a d i a b a t i c f r a m e w o r k the c o n t r i b u t i o n f r o m H e { v a n i s h e s while
t h e c o n t r i b u t i o n f r o m the t e r m v -V R b e c o m e s d o m i n a n t . P h y s i c a l l y this
i s due to the f a c t that n e a r an avoided c r o s s i n g the m o l e c u l a r wave
f u n c t i o n v a r i e s r a p i d l y with the i n t e r n u c l e a r d i s t a n c e . On the o t h e r hand,
the c o n t r i b u t i o n f r o m r o t a t i o n a l coupling will be s i m i l a r to that in the
diabatic representation.
IAEA-SMR-12/26, 27 663
e(R)
FIG. 19. Schematic diabatic curve crossing.
The c h o i c e of a d i a b a t i c o r an a d i a b a t i c r e p r e s e n t a t i o n d e p e n d s on the
p r o b l e m u n d e r i n v e s t i g a t i o n . Of c o u r s e , if enough s t a t e s a r e included in
the e x p a n s i o n , the two m e t h o d s will be e q u i v a l e n t , but in p r a c t i c e we t r y
to r e s t r i c t the e x p a n s i o n to t h r e e o r four s t a t e s . B e s i d e s , s i n c e q u a n t i t a -
tive c a l c u l a t i o n s a r e out of q u e s t i o n in m a n y c o m p l e x s y s t e m s , it is
i m p e r a t i v e f o r a q u a l i t a t i v e i n t e r p r e t a t i o n to u s e a p h y s i c a l l y m e a n i n g f u l
expansion.
To i l l u s t r a t e the s i t u a t i o n , let us c o n s i d e r two t y p i c a l d i a b a t i c e n e r g y
c u r v e s a s given in F i g . 1 9 . Let us denote by ei(R), £2(R) the e n e r g y c u r v e s
of the two d i a b a t i c s t a t e s , and let Hi2(R) = <C Ф 11H eC jф 2 / • T h e n , s u p p o s i n g
the a d i a b a t i c s t a t e s m a y be c o n s i d e r e d as a l i n e a r c o m b i n a t i o n of and
ip2, it is e a s y to show that at the d i a b a t i c c r o s s i n g point the a d i a b a t i c
e n e r g i e s will d i f f e r by 2Hi2- We thus see t h a t , if the m a t r i x e l e m e n t
Hj2 i s l a r g e (e.g. of the s a m e o r d e r a s ez(°°) - ei(°°)), the a d i a b a t i c r e p r e -
s e n t a t i o n is to be p r e f e r r e d in the c o l l i s i o n p r o b l e m . On the o t h e r hand,
if Hi2 is s m a l l , the p r o b a b i l i t y of a t r a n s i t i o n f r o m d i a b a t i c s t a t e 1 to
d i a b a t i c s t a t e 2 is s m a l l ; a d i a b a t i c r e p r e s e n t a t i o n is to be p r e f e r r e d .
T h u s when H 1 2 is v e r y s m a l l o r v e r y l a r g e , the p r o b a b i l i t y of an i n e l a s t i c
t r a n s i t i o n is s m a l l .
In g e n e r a l , a m u l t i - s t a t e e x p a n s i o n i s n e c e s s a r y to e x a m i n e any given
s y s t e m . But m a n y f e a t u r e s of i n e l a s t i c t r a n s i t i o n s can be s a t i s f a c t o r i l y
t r e a t e d on a t w o - s t a t e b a s i s . T h e r e a r e t h r e e p a r t i c u l a r l y i n t e r e s t i n g
c a s e s depending on w h e r e the c r o s s i n g point RQ o c c u r s at
(i) u n i t e d - a t o m s l i m i t ,
(ii) i n t e r m e d i a t e i n t e r n u c l e a r s e p a r a t i o n s (~ 2ao),
(iii) s e p a r a t e d - a t o m s l i m i t .
R o t a t i o n a l coupling is the m o s t f r e q u e n t in c a s e s (i) and (iii) while

r a d i a l coupling u s u a l l y a r i s e s f o r c a s e (ii). But t h e r e is no a b s o l u t e r u l e .
Let us c o n s i d e r c a s e (ii), with the c r o s s i n g point at P ( F i g . 2 0 ) .
The r e a c t i o n A -> В m a y t h u s p r o c e e d via two p o s s i b l e p a t h s A - P - C - P - B
o r A - P - D - P - B . Away f r o m the c r o s s i n g , the s y s t e m e v o l v e s a d i a -
b a t i c a l l y , so t h a t the m a i n d i f f e r e n c e b e t w e e n the two r e a c t i o n p a t h s i s the
p h a s e d i f f e r e n c e b e t w e e n P C and P D . The d i f f e r e n t i a l s c a t t e r i n g c r o s s -
s e c t i o n f o r the e x c i t a t i o n of В will thus exhibit a t y p i c a l i n t e r f e r e n c e
664 McCARROLL
£(R)
FIG. 20. Typical two-channel excitation process.
p a t t e r n . On the o t h e r h a n d , f o r a type-(i) c r o s s i n g , no such i n t e r f e r e n c e

" o c c u r s . T y p e - ( i i i ) c r o s s i n g s o c c u r f r e q u e n t l y in the exit c h a n n e l s but
r a r e l y in the e n t r y c h a n n e l . C o n s e q u e n t l y they have little e f f e c t on the
a n g u l a r v a r i a t i o n of the d i f f e r e n t i a l s c a t t e r i n g c r o s s - s e c t i o n . On the o t h e r
hand, they a f f e c t c o n s i d e r a b l y the e n e r g y v a r i a t i o n of the t o t a l c r o s s -
section.
3. PARTICULAR EXAMPLES
3.1. The s y s t e m H + - H
The p r i m a r y e x c i t a t i o n m e c h a n i s m in H + - H c o l l i s i o n s a r i s e s f r o m
the r o t a t i o n a l coupling of the 2рстu s t a t e with the 2p7ru s t a t e at s m a l l
i n t e r n u c l e a r s e p a r a t i o n s . The c o r r e s p o n d i n g m a t r i x e l e m e n t
L 2pn (3.1)
2po R2 У'
can of c o u r s e be c a l c u l a t e d exactly f o r a l l i n t e r n u c l e a r d i s t a n c e s , but

s i n c e the t r a n s i t i o n p r o b a b i l i t y i s l a r g e only when the e n e r g y c u r v e s
of the 2pcru and 2p7ru s t a t e s a r e c l o s e , it t u r n s out t h a t the m a t r i x e l e m e n t
(3.1) i s r e q u i r e d with a c c u r a c y only at s m a l l i n t e r n u c l e a r d i s t a n c e s .
Indeed l i t t l e e r r o r i s c a u s e d in r e p l a c i n g (3.1) by its u n i t e d - a t o m s l i m i t ,
namely - ihb/R2.
T h u s e x p a n d i n g the wave function Ф а (г, t) on a b a s i s s e t of the I s a g ,
2 p a u , 2p7Tu s t a t e s , denoted r e s p e c t i v e l y by s u b s c r i p t s 1, 2, 3
Ф(г, t) « j ( t ) l M r . t) (3.2)
I
we o b t a i n f o r the s y m m e t r i c (g) s t a t e s
iàj = e^R)«! (3.3)

IAEA-SMR-12/26, 27 665
and f o r the a n t i s y m m e t r i c (u) s t a t e s
i OR G = E 2 ( R ) A 2 + F 2 3 A 3
i á 3 = e 3 ( R) a 3 + F 3 2 a 2 (3.4)
s u b j e c t to the b o u n d a r y c o n d i t i o n s
ai(-°o)= l i m - i - e x p -J - i j e^RJdť
t->-oo -J 2
a2(-co) - lim — e x p -j - i j e2(R)dť
ot 3 ( =0 (3.5)
where
F (3.6)
23 = F ^2 = Ц Т t1"8^)]
w h e r e S(R) b e h a v e s a s R 2 f o r s m a l l R.
The s o l u t i o n of (3.3) i s i m m e d i a t e , yielding
öl(0C) = eXP kliR) ei(0

(3.7)
J " °)ldt}
On t h e o t h e r h a n d , E q . ( 3 . 4 ) c a n only b e s o l v e d by n u m e r i c a l m e a n s ( f o r
e x a m p l e by t h a t of B u l i r s c h and S t o e r (1966)).
H a v i n g d e t e r m i n e d a^ (°o) a s a f u n c t i o n of the i m p a c t p a r a m e t e r b,
t h e v a r i o u s c r o s s - s e c t i o n s m a y be c o m p u t e d . T h u s the d i f f e r e n t i a l
s c a t t e r i n g c r o s s - s e c t i o n f o r e l a s t i c s c a t t e r i n g ст^ and t h a t f o r r e s o n a n t
c h a r g e e x c h a n g e c r " a r e g i v e n by
a í - e x ( 0 ) = ЦУ' j~ b A^' e x (b) J 0 (2p b v s i n 6/2) db (3.8)
where
A ^ ' " = J- {(»!(») ± ff2(«>)} (3.9)

v2
It s h o u l d be r e m a r k e d t h a t with the d e f i n i t i o n s u s e d in t h i s w o r k , the

C o u l o m b i n t e r a c t i o n b e t w e e n the n u c l e i m u s t be i n c l u d e d in e ; ( R ) . If, a s
i s o f t e n the c a s e , the C o u l o m b t e r m i s o m i t t e d , an a d d i t i o n a l p h a s e
f a c t o r b i 2 Z Z ' / v m u s t be i n t r o d u c e d in (3.8), w h e r e Z , Z ' a r e the n u c l e a r
c h a r g e s (both e q u a l to 1 in t h e p r e s e n t c a s e ) .
666 McCARROLL
0 1 2 3 4 5 6 7 8 9
R (arb. u n i t s )
FIG. 21. Potential energy curves for Нг (Bransden (1970)).
T h e only i n e l a s t i c p r o c e s s allowed f o r in the c a l c u l a t i o n is t h a t a r i s i n g

f r o m t h e 2p7ru s t a t e which d i s s o c i a t e s to yield H+ and H(2p). H o w e v e r , it
i s e v i d e n t f r o m the c o r r e l a t i o n d i a g r a m of Hg (see F i g . 2 1 ) t h a t at l a r g e
i n t e r n u c l e a r s e p a r a t i o n s the 2ря-и state will be r o t a t i o n a l l y coupled to the
Зрсти and the 4fu u s t a t e s , which d i s s o c i a t e to the s a m e s e p a r a t e d - a t o m s
l i m i t . The p r o b a b i l i t y аз(°°) w i l l t h e r e f o r e yield a s u m of c r o s s - s e c t i o n s
f o r e x c i t a t i o n into the 2s o r 2p s t a t e . H o w e v e r , c a l c u l a t i o n s by
G a u s s o r g u e s and Salin (1971), using an a t o m i c e x p a n s i o n which t a k e s
a c c o u n t of the l o n g - d i s t a n c e c r o s s i n g s , i n d i c a t e that d i s s o c i a t i o n of the
2р7г s t a t e t a k e s p l a c e p r i n c i p a l l y into the p ± 1 s t a t e (quantized with r e s p e c t
to the d i r e c t i o n of the i n c i d e n t b e a m ) . T h u s we m a y w r i t e the c r o s s -
section for excitation as
a2'ex (0) = UV I J 2
b a 3 ( b ) J x (2m v b s i n 0 / 2 ) d b | 2 (3.10)
о
In o r d e r to c o m p a r e the c a l c u l a t e d q u a n t i t i e s with e x p e r i m e n t it is
u s e f u l to d e f i n e the p r o b a b i l i t y for resonant charge exchange
PlT = ff" ( e )/ CT t («) (3.11)

IAEA-SMR-12/26, 27 667
where
CTd . „ex , d +, „ex . г..

1 1 2 2 (o.lá)
The p r o b a b i l i t y f o r c a p t u r e into the 2p s t a t e is

СЛ
-, ex CT2 (в)
Pip = ' Zia\
0r t (6) (ЗЛЗ)
and the t o t a l p r o b a b i l i t y f o r c h a r g e exchange is
p e x = p ex + pex (3 14)
A s e l e c t i o n of the t h e o r e t i c a l r e s u l t s and a c o m p a r i s o n with e x p e r i m e n t

i s given in F i g s 22 - 26. It is of p a r t i c u l a r i n t e r e s t to note that when n o n -
a d i a b a t i c e f f e c t s b e c o m e i m p o r t a n t (E6 s 1 keV X d e g r e e ) , the o s c i l l a t i o n s
of P e x u n d e r g o a change of p h a s e c o m p a r e d with a p u r e l y a d i a b a t i c m o d e l .
Such a p h e n o m e n o n is c h a r a c t e r i s t i c of r o t a t i o n a l coupling.
To s e e this m o r e c l e a r l y , let us c o n s i d e r the c a s e of c l o s e c o l l i s i o n s ,
w h o s e c r o s s - s e c t i o n is p r i m a r i l y d e t e r m i n e d by s m a l l i m p a c t p a r a m e t e r s .
F o r s m a l l b the coupling t e r m s will be n o n - n e g l i g i b l e only f o r s m a l l R,
a l l o w i n g u s to s e t S(R) = 0 and ~ ^з • Then m a k i n g the s u b s t i t u t i o n
e x
2,3 = « 2 , 3 P ]i / ez(R)dty (3.15)
we o b t a i n
.
c
_ vb c
2 - R 2 3
(3.16)
vb
R2 °2
which h a s f o r solution
vt vt
J b ü +v^t2 R
(3.17)
b b
3
" Jb2 +V2t2 " R
T h u s , f o r s m a l l v a l u e s of vt, the m a i n e f f e c t of r o t a t i o n a l coupling is to

induce a change of p h a s e of тт in c 2 a s vt g o e s f r o m n e g a t i v e to p o s i t i v e
v a l u e s . T h i s e x p l a i n s why in the a d i a b a t i c a p p r o x i m a t i o n the o s c i l l a t i o n s
of P e x a s a f u n c t i o n of e n e r g y f o r l a r g e в a r e e x a c t l y out of p h a s e with
t h o s e p r e d i c t e d by n o n - a d i a b a t i c c a l c u l a t i o n s .
3.2. The H e ^ - H e s y s t e m
T h e H e + - H e s y s t e m i s p a r t i c u l a r l y i n t e r e s t i n g s i n c e it is s u f f i c i e n t l y
c o m p l e x to be t y p i c a l of a l a r g e c l a s s of i o n - a t o m c o l l i s i o n s and yet
6 6 8 McCARROLL
0.1 0.2 0.5 I 20.1 0.2 0.5 I 2

Incident proton energy E (keVJ
FIG. 22. Charge exchange probabilities P | p (dashed line) and P e x (solid line) as functions of the incident
proton energy for different scattering angles. Experimental results of Helbig and Everhart, 1965 (empty
circles) (McCarroll and Piacentini (1910)).
FIG. 23. Theoretical charge exchange probabilities P®* (dashed line) P 2 p their sum P e x (solid line)
as a function of scattering angle for energies of 700 eV and 1 keV. О and Д : experimental results of
Helbig and Everhart. Also plotted are the computed values of P e x (dash-dot curve) in the adiabatic
approximation (McCarroll and Piacentini (1970)).
s u f f i c i e n t l y s i m p l e to be a m e n a b l e to q u a n t i t a t i v e t h e o r e t i c a l c a l c u l a t i o n s .
F u r t h e r m o r e , the He + - H e s y s t e m has b e e n the s u b j e c t of e x t e n s i v e
experimental investigation.
Let us e x a m i n e the d i a b a t i c c o r r e l a t i o n d i a g r a m . The s e p a r a t e d a t o m s
He + ( l s ) + H e ( l s 2 ) 1 S g i v e s r i s e to two m o l e c u l a r s t a t e s the {lscr| 2pcr u )X 2 £ u
s t a t e and the (lscr„ 2po-§)A 2 Eg s t a t e . T h e X 2 £ u s t a t e is c o r r e l a t e d in the
IAEA-SMR-12/26, 27 669
FIG. 24. Mapping of the experimental (full circles) and theoretical (solid line) maxima, and experimental
(empty circles) and theoretical (dashed line) minima of the charge exchange probability P e x in the (E,0)
plane (McCarroll and Piacentini (1970)).
FIG. 25. Energy-loss spectrum of H + on H at an incident energy of 1 keV and scattering angle of 1°. The
widths of the two peaks (elastic and inelastic) are almost equal which indicates that the n=2 level is the
only one substantially excited. The energies of the excited levels of H atoms are indicated (Houver et al. (1972)).
u n i t e d - a t o m s l i m i t to B e + ( l s 2 2 p ) 2 P w h i l s t the A 2 E g s t a t e is c o r r e l a t e d to
Be + ( l s 2 p 2 ) 2 D . The e n e r g y c u r v e of the A 2 E g thus c r o s s e s a s e r i e s of
e n e r g y c u r v e s of the s t a t e s ( l s o | n i c r g ) 2 E g , which d i s s o c i a t e to
He + ( l s ) + H e ( l s , n í ) . T h u s e x c i t a t i o n of He t a k e s p l a c e by r a d i a l coupling
of the 2 E g s t a t e s . The f i r s t d i r e c t e v i d e n c e of t h i s e x c i t a t i o n m e c h a n i s m
w a s found by L o r e n t s e t a l . (1966), who m e a s u r e d the d i f f e r e n t i a l s c a t t e r i n g
c r o s s - s e c t i o n f o r e x c i t a t i o n of the 2 3 S s t a t e of He ( F i g . 3 0 ) .
At c l o s e i n t e r n u c l e a r s e p a r a t i o n s r o t a t i o n a l coupling b e c o m e s an
i m p o r t a n t e x c i t a t i o n m e c h a n i s m . The X 2 E U s t a t e is r o t a t i o n a l l y coupled
670 McCARROLL
10'
10'
0 1 2 3 U 5 6 7
S l a b t c l e g.)
+
FIG. 26. Differential cross-sections for H-H collisions at an incident energy of 500 eV. Elastic scattering
(solid line), charge exchange (dashed line), excitation (dotted line); theoret. curves after McCarroll et al.
and Chen et al. (Houver et al. (1912)).
to t h e ( l s 0 2 2 p i r u )2 Hu s t a t e w h i l e t h e 2 £ g s t a t e i s c o u p l e d t o t h e
( l s o g 2pcru 2p7Tu ) 2 n g a n d the ( l s a g 2ртг2 )2д s t a t e s . T h e p o s s i b l e d i s s o c i a -
t i o n p r o d u c t s of t h e s e s t a t e s a r e s u m m a r i z e d a s f o l l o w s :
(lSCTg22p7Tu)2nu - He + (ls) + He (Is, 2p) 1 - 3 P

(3.18)
( 2 1 . 2 , 21.0 eV)
В
[{(lSCTg2P7ru ) 3 £ J 2рсти] 2 n g - He + (ls) + He (Is, 2p) 1 - 3 P
(3.19)
(21.2, 21.0 eV)
U(lS0g2pcr11)1i;il}2p7ru]2ng - H e + ( 2 p ) + He ( l s 2 ) 1 S (3.20)
(40.8 eV)
- H e 2 + + He ( l s 2 ) 1 S + e
(3.21)
(> 54.4 eV)
[IsCTg 2р7г 2 ] 2 Дg - He (Is, 2p) + He + (2p)

(3.22)
( 6 2 . 0 , 61.8 eV)
D
- He*(2p2)1S1D + He+(ls)
(3.23)
( 6 0 . 1 , 6 2 . 1 eV)
I A E A - S M R - 1 2 / 2 6 , 27 671
It is of i n t e r e s t to o b s e r v e that e x c i t a t i o n of H e ( l s , 2 p ) m a y p r o c e e d e i t h e r
v i a the 2 E U s t a t e o r via the 2 Eg s t a t e . I n t e r f e r e n c e b e t w e e n the two
e x c i t a t i o n m o d e s w i l l t h e r e f o r e lead to s t r u c t u r e in the c o r r e s p o n d i n g
d i f f e r e n t i a l s c a t t e r i n g c u r v e . Of c o u r s e e x c i t a t i o n of H e ( l s , 2p) m a y a l s o
o c c u r by an e l e c t r o n i c t r a n s i t i o n by r a d i a l coupling of the 2 E g s t a t e to
the (Is0g 2 3d0g ) 2 E g s t a t e at the c r o s s i n g point of t h e i r r e s p e c t i v e p o t e n t i a l
e n e r g y c u r v e s at R ^ 2 a o . H o w e v e r , this m e c h a n i s m , which h a s its
m a x i m u m e f f e c t at s m a l l a n g l e s E0 % 0.6 keV X d e g r e e , is m u c h l e s s
e f f i c i e n t than r o t a t i o n a l coupling f o r l a r g e a n g l e s , E0 ě 4 keV X d e g r e e .
It should a l s o be noted that the d i s s o c i a t i o n p r o d u c t s of the 2 Пg s t a t e
d e p e n d s on the spin s t a t e of the ( l s a g 2pcr u ). It is e a s y to show f r o m
s y m m e t r y c o n s i d e r a t i o n that in the t r i p l e t s t a t e the c o r e d i s s o c i a t e s a s
He| + (lsCTg2pa u ) 3 E u - He + ( l s ) + He + ( l s ) (3.24)
while the s i n g l e t s t a t e d i s s o c i a t e s a s
H e ^ l s a ž p a j 1 E u - He 2 + + He ( I s 2 ) J S (3.25)
The d i s s o c i a t i o n p r o d u c t s of the 2 n g s t a t e a r e then a s in (3.19), (3.20),

(3.21).
But p e r h a p s the m o s t s t r i k i n g f e a t u r e of r o t a t i o n a l coupling is the
highly s e l e c t i v e n a t u r e of the e x c i t a t i o n c o m p a r e d with r a d i a l coupling.
In addition c e r t a i n of the r e a c t i o n p r o d u c t s a r e quite u n e x p e c t e d .
T h e r e a r e t h r e e m a i n t y p e s of ionization p r o c e s s e s . The u n i t e d -
a t o m s l i m i t B e + ( l s 2 p 2 ) o f the A 2 Eg s t a t e is s u b j e c t to a u t o i o n i z a t i o n ,
which c o r r e s p o n d s to r a d i a l coupling with the 2 E g continuum s t a t e s of
He^. The s i t u a t i o n i s r e p r e s e n t e d s c h e m a t i c a l l y in F i g . 2 7 .
R o t a t i o n a l coupling l e a d s to ionization via the e x c i t a t i o n of He*(2p 2 )
which i s s u b j e c t to a u t o i o n i z a t i o n . The d i r e c t i o n i z a t i o n p r o c e s s (E)
f o r the f o r m a t i o n of He 2 + is e x p e c t e d to be v e r y w e a k .
A complete theoretical formulation, taking account simultaneously
of both r o t a t i o n a l and r a d i a l coupling, h a s not b e e n c a r r i e d o u t . O u r know-
ledge of the m o l e c u l a r s t a t e s of He£ is not yet s u f f i c i e n t f o r s u c h c a l c u l a -
t i o n s to be w o r t h - w h i l e . F o r t u n a t e l y the m a i n q u a n t i t a t i v e a s p e c t s c a n be
t r e a t e d s i m p l y . R a d i a l coupling i s i m p o r t a n t f o r E0 s 4 keV X d e g r e e ,
while r o t a t i o n a l coupling is d o m i n a n t f o r E 0 ž 4 keV X d e g r e e . The r o t a -
t i o n a l coupling m a t r i x e l e m e n t s can be w e l l a p p r o x i m a t e d by t h e i r u n i t e d -
a t o m s l i m i t and the c o r r e s p o n d i n g coupled e q u a t i o n s solved in m u c h the
s a m e way a s f o r H + - H . The d e t a i l s a r e given by M c C a r r o l l and
P i a c e n t i n i (1971). H o w e v e r , in o r d e r to i l l u s t r a t e the p r o b l e m , it is
b e s t to e x a m i n e the e x p e r i m e n t a l r e s u l t s .
F i g u r e 28 shows an e n e r g y l o s s s p e c t r u m i l l u s t r a t i n g c l e a r l y e l a s t i c
s c a t t e r i n g A and the i n e l a s t i c r e a c t i o n s B, C, D. With i m p r o v e d r e s o l u -
tion the a n a l y s i s of peak В s h o w s two well s e p a r a t e d p e a k s : B^ c o r r e s -
ponding to e x c i t a t i o n of the n = 2 l e v e l s and B2 c o r r e s p o n d i n g to e x c i t a t i o n
of l e v e l s n ë 3. The t a i l t o w a r d s h i g h e r e n e r g y l o s s e s c o r r e s p o n d s to
i o n i z a t i o n . H o w e v e r , it i s of p a r t i c u l a r i n t e r e s t to e x a m i n e the evolution
of the s p e c t r u m a s a f u n c t i o n of angle (Fig.29).
F o r E0 ^ 0.6 keV X d e g r e e , the n = 2 l e v e l s a r e m a i n l y e x c i t e d , the
f i r s t few E - E c r o s s i n g s only b e i n g a t t a i n e d . B e t w e e n 0.6 and
2.0 keV X d e g r e e a l l the E - E c r o s s i n g s a r e r e a c h e d and e x c i t a t i o n of
672 McCARROLL
Г He+C2p) + Не (Is 2р) |,3

р
j He+cts)-»- Не C2p 2 j's. 'd
FIG,27. Schematic correlation diagram for the H e + - H e system. A, {(lsOg) 2 (2po u )} 2 £ u ;

B, {(lsog) z (2so g )} 2 £ g ; C, {(lso g ) 2 (2 P 7r u )} 2 n u ; D, {(lso g ) 2 (3do_) 2 Z g ; E, {(lso g ) 2 } ' E g ( o f H e f ) ;
F. {(lso g )(2po u ) 2 } ! £ g ; G, {((lso g )(2po u ) 3 E u )(2p T u )} 2 n g i H. {((lso g )(2po u ) 1 £и)(2ртги)} 2I1 ;
J, {(lso g )(2p7r u ) 2 } 2 A g ; К, { ( ^ х г р О ц ^ ' Е ц (of Нег + ). Z-states (solid line); П-states (dashed line);
Д-states (dotted line). Curve crossings where radial coupling induces inelastic transitions are marked by
full circles; those where rotational coupling occurs are marked by squares (Barat et al. (1972)).
the h i g h e r l e v e l s b e c o m e s of c o m p a r a b l e i m p o r t a n c e to e x c i t a t i o n of the
n = 2 l e v e l s . C l o s e to т = 2 keV X d e g r e e , coupling with the continuum
a p p e a r s to be m a x i m u m and s o m e s t r u c t u r e i s v i s i b l e in the continuum
e n e r g y d i s t r i b u t i o n . With i n c r e a s i n g a n g l e , the r a d i a l v e l o c i t y in the
v i c i n i t y of the E - E c r o s s i n g s i n c r e a s e s and the c o r r e s p o n d i n g t r a n s i -
tion p r o b a b i l i t i e s d e c r e a s e . T h i s e f f e c t i s c o n f i r m e d by the d i s a p p e a r a n c e
of p e a k B2 and the i o n i z a t i o n t a i l when т e x c e e d s 3 keV X d e g r e e .
On the o t h e r h a n d , the t u r n i n g point a p p r o a c h e s the u n i t e d - a t o m s
l i m i t and r o t a t i o n a l coupling to the e x c i t e d n u , Hg and A g s t a t e s b e c o m e s
the d o m i n a n t e x c i t a t i o n m e c h a n i s m . T h u s of the s i n g l y e x c i t e d s t a t e s only
the ( I s 2p) ! ' 3 P s t a t e i s e x c i t e d .
I A E A - S M R - 1 2 / 2 6 , 27 673
FIG.28. Energy loss spectra for H e + - H e at 1 keV for various scattering angles (Barat et al. (1912)).
FIG. 29. Differential cross-sections for He + -He collisions as a function of т for incident ion energy of
1 keV. Curve A is the elastic cross-section, curves Bi and Bz are respectively the inelastic cross-section
of the n = 2 levels and for excitation of the n > 2 levels of He (Barat et al. (1972)).
674 McCARROLL
FIG. 30, Differential cross-section for excitation of He(2 3 S) in He + -He collisions at 600 eV
(Lorents et al. (1966)).
FIG. 31. Differential cross-sections for He + -He collisions as a function of т for incident ion energies
of (a) 2 keV and (b) 3 keV. Curve A designates the elastic cross-section, curve В (sum of В j and B2
defined in Fig. 29) the single excitation cross-section of He, curve С the excitation cross-section of
the n = 2 level of He + , curve D the double excitation cross-section of He, and curve E the cross-section
for the formation of He 2 . The bump on the curve В for large r is real. It had previously been observed
with an entirely different apparatus (Baudon et al. (1968); Barat et al. (1912).)
I A E A - S M R - 1 2 / 2 6 , 27 675
T h e r a p i d d e c r e a s e of the c r o s s - s e c t i o n B2 c o m p a r e d with t h a t f o r
B.i i l l u s t r a t e s c l e a r l y how the Z - £ c r o s s i n g s b e c o m e of s e c o n d a r y
i m p o r t a n c e f o r l a r g e - a n g l e s c a t t e r i n g . The o s c i l l a t o r y b e h a v i o u r of the
c u r v e B i c o n f i r m s the p r e d i c t i o n that e x c i t a t i o n by r o t a t i o n a l coupling
can p r o c e e d e i t h e r via the 2 £ u - 2 n u t r a n s i t i o n . I n t e r f e r e n c e b e t w e e n the
two e x c i t a t i o n m o d e s l e a d s to s t r u c t u r e in the c o r r e s p o n d i n g d i f f e r e n t i a l
c r o s s - s e c t i o n c u r v e (see a l s o F i g . 3 0 ) .
The e n e r g y l o s s peak c o r r e s p o n d i n g to p r o c e s s С at an e n e r g y l o s s
of about 40 eV is m i x e d with the ionization t a i l . As a c o n s e q u e n c e , the
c r o s s - s e c t i o n cannot be o b t a i n e d with such p r e c i s i o n a s that f o r p r o c e s s e s
В o r D (see also Fig.31).
The e n e r g y l o s s peak D c o r r e s p o n d s e i t h e r to e x c i t a t i o n of the a u t o -
ionizing s t a t e He*(2p 2 ) o r to s i m u l t a n e o u s e x c i t a t i o n of the t a r g e t and the
i n c i d e n t p a r t i c l e . New m e a s u r e m e n t s using t i m e - o f - f l i g h t t e c h n i q u e s
should soon d e t e r m i n e which of the p r o c e s s e s i s the m o r e i m p o r t a n t .
T h e e n e r g y l o s s p e a k E due to the f o r m a t i o n of doubly ionized He
is c o n f i r m e d . H o w e v e r , the p r o b a b i l i t y is v e r y w e a k .
F r o m the e n e r g y l o s s s p e c t r a , it is p o s s i b l e to d e t e r m i n e the d i s t r i -
bution in e n e r g y E e j of the e j e c t e d e l e c t r o n s c o r r e s p o n d i n g to a given
s c a t t e r i n g angle of the i n c i d e n t p a r t i c l e . The m a x i m u m of this d i s t r i b u t i o n
s h i f t s to l a r g e r v a l u e s of E e ? a s т i n c r e a s e s (Fig.32).
With i n c r e a s i n g т, a s e c o n d m a x i m u m a p p e a r s f o r s m a l l E e j , which
in i t s t u r n a l s o s h i f t s t o w a r d l a r g e r v a l u e s of E e j as r i n c r e a s e s . The
following i n t e r p r e t a t i o n is s u g g e s t e d (see F i g . 3 3 ) . The 2 £ g c u r v e e n t e r s
the c o n t i n u u m f o r R š R j ( c u r v e A). The c o n t i n u u m c o r r e s p o n d s to the
FIG. 32. Energy distribution of electrons produced by ionization in He + -He collisions for (a) 500 eV
and (b) 1 keV at different scattering angles of the incident beam (Barat et al. (1972)).
6 7 6 McCARROLL
FIG. 33. Schematic representation of the crossings of the potential energy curve; A of the 1 £g state
of Нег with those of the continuum 2 £ g states of the system (He*4" + e). Curve В represents the
continuum state where the free electron has zero energy. Curve С (a, b, c) represent the continuum states
where the energy of the free electron is respectively E'eç, The crossings occur at RI, Ri', RJ".
For E i t < < E™ , r ; > RJ' > R™ (Barat e t al. (1942)).
2 1 2+
( l s o g ) E s t a t e of Нег + f r e e e l e c t r o n ( c u r v e B). The c u r v e С obtained
f r o m c u r v e В by adding t h e e n e r g y E e j f o r e a c h value of R c r o s s the
c u r v e A f o r R = R'j. We s u p p o s e then that t r a n s i t i o n s to the continuum
with p r o d u c t i o n of an e l e c t r o n of e n e r g y E e j o c c u r a t the c r o s s i n g . T h e
d i f f e r e n t i a l c r o s s - s e c t i o n f o r t h i s r e a c t i o n h a s t h e r e f o r e the s a m e
o s c i l l a t o r y b e h a v i o u r a s in the c a s e of c u r v e c r o s s i n g b e t w e e n two d i s c r e t e
l e v e l s . As E e { i n c r e a s e s , R j d e c r e a s e s and the c u r v e f o r the d i f f e r e n t i a l
c r o s s - s e c t i o n is s h i f t e d to h i g h e r v a l u e s of т. T h e n , it i s r e a d i l y s e e n
that t h e d i f f e r e n t i a l c r o s s - s e c t i o n a s a f u n c t i o n of E e { f o r fixed т has a
s t r u c t u r e s i m i l a r to that o b s e r v e d .
ACKNOWLEDGEMENTS
I w i s h to thank D r . A. R i e r a f o r h i s c o n t r i b u t i o n to s e c t i o n 2.2 and

D r . R.D. P i a c e n t i n i f o r a c r i t i c a l r e a d i n g of the m a n u s c r i p t .
BIBLIOGRAPHY
General
BATES, D. R., Atomic and Molecular Processes, Academic Press, New York (1962).
BRANSDEN, В. H . , Atomic Collision Theory, Benjamin Inc. New York (1910).
GLAUBER, R, (1959) 'Lectures in Theoretical Physics' (BRITTEN, W . E , , DUNHAM, L. G . , Eds) 1 315.
MCDOWELL, M . R . C . , COLEMAN, J.P., Introduction to the Theory of Ion-Atom Collisions, North

Holland, Amsterdam (1970).
MASSEY, H. S. W . , Electronic and Ionic I m p a c t Phenomena Vol. HI. Slow Collisions of Heavy Particles,
Oxford (1970).
I A E A - S M R - 1 2 / 2 6 , 27 677
MOTT, N . F . , MASSEY, H. S . W . , The Theory of Atomic Collisions, Third Edition, Oxford (1965).
NEWTON, R . G . , Scattering Theory of Waves and Particles, McGraw-Hill, New York (1966).
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BARAT, M . , LICHTEN, W. (1912) Phys. Rev. A 6 211.
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Colorado, p. 93.
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BULIRSCH, R., STOER, J. (1966) Numerische Math. 8 1.
DHUICQ, D. , BAUDON, J . , BARAT, M. (1973) J. Phys. B: Atom. Molec. Phys. 6 LI.
FELTGEN, R., PAULY, H . , TORELLO, F., VEHMEYER, H. (1973) Phys. Rev. Lett. 30 820.
FIRSOV, O.B. (1953) Zh. Eksp. Teor. Fiz. 24 279.
FORD, K. W . , WHEELER, J. A. (1959) Ann. Phys. (N.Y. ) U 259.
FRANÇOIS, R., DHUICQ, D . , BARAT, M. (1972) J. Phys. B: Atom. Molec. Phys. 5 963.
GAUSSORGUES, C . , SALIN, A. (1971) J. Phys. B: Atom. Molec. Phys. 4 503.
GERSHTE1N, S . S . , KRIOCHEN KOV, V. D. (1961) Sov. Phys. JETP, 13 1044.
HELBIG, H.F. , EVERHART, E. (1965) Phys. Rev. 140 A715.
HOUVER, J . C . , FAYETON, J . , ABIGNOLI, M . , BARAT, M. (1912) Phys. Rev. Lett. 28 1433.
HUND, F. (1927) Z. Phys. 40 742.
LICHTEN, W. (1967) Phys. Rev. 164 131.
LORENTS, D . C . , ABERTH, W . , HESTERMAN. V.W. (1966) Phys. Rev. Lett. 17 849.
McCARROLL, R., SALIN, A. (1968) J. Phys. B: Atom. Molec. Phys. 3 1336.
McCARROLL, R., PIACENTINI, R.D. (1970) J. Phys. B: Atom. Molec. Phys. 3 1336.
McCARROLL, R., PIACENTINI, R.D. (1971) J. Phys. B: Atom. Molec. Phys. 4 1026.
MORSE, P . M . , STÜCKELBERG, E. (1929) Phys. Rev. 33 932.
MULLIKEN, R. S. (1928) Phys. Rev. 32 186.
NEUMANN, W . , PAULY, H. (1910) J. Chem. Phys. 52 2548.
NIKITIN, E. E. (1968) Chemische Elementarprozesse (HARTMANN, H . , Ed.), Springer-Verlag.
NIKITIN, E . E . , OVCHINNIKOVA, M. Ya. (1912) Sov. Phys. Uspekhi 14 394.
PAULY, H . , TOENN1ES, J. P. (1965) Adv. At. Mol. Phys. 1 195.
ROSENTHAL, H . , FOLEY, H.M. (1969) Phys. Rev. Lett. 23 1480.
SMITH, F. T . , MARCHI, R. P. , ABERTH, W . , LORENTS, D. C . , HEINZ, O. (1967) Phys. Rev. 161 31.
IAEA-SMR-12/50
PHOTOIONIZATION
M. GAVRILA
Department of Physics,
University of Bucharest,
Bucharest, Romania
Abstract
PHOTOIONIZATION.
1. General low-energy formulas; 2. Hydrogen-like atoms; 3. Two-electron atoms (helium and
positive ions, H" ions).
INTRODUCTION
T h e p h o t o e f f e c t i s t h e p r o c e s s by which an i n c o m i n g photon e j e c t s an
e l e c t r o n out of an a t o m i c s y s t e m . It h a s p l a y e d an i m p o r t a n t h i s t o r i c a l
r o l e in t h e d i s c o v e r y of t h e q u a n t u m s t r u c t u r e of l i g h t ( E i n s t e i n 1905).
The binding of t h e e l e c t r o n is e s s e n t i a l f o r the p r o c e s s to take p l a c e .
Indeed, a f r e e e l e c t r o n c a n n o t a b s o r b a photon b e c a u s e c o n s e r v a t i o n of
e n e r g y and m o m e n t u m c a n n o t be s a t i s f i e d at t h e s a m e t i m e . H o w e v e r , f o r
a b o u n d e l e c t r o n , only e n e r g y c o n s e r v a t i o n n e e d be s a t i s f i e d :
E = úo - I
w h e r e E = p 2 / 2 m is t h e k i n e t i c e n e r g y of t h e e m i t t e d e l e c t r o n and I is the
i o n i z a t i o n p o t e n t i a l c o r r e s p o n d i n g to t h e i n i t i a l s t a t e . T h i s is the w e l l -
Einstein equation.
T h e r e a r e v a r i o u s t y p e s of p h o t o e f f e c t a c c o r d i n g to t h e type of a t o m i c
s y s t e m in which the e l e c t r o n is bound ( a t o m , m o l e c u l e , c r y s t a l , e t c . ) . In
t h e following, we s h a l l only c o n s i d e r t h e c a s e of t h e i s o l a t e d atom. The
r e s u l t s t h u s d e r i v e d will obviously apply to m ono a t o m i c g a s e s . H o w e v e r ,
they will a l s o apply, in g e n e r a l , to the photoionization of the i n n e r a t o m i c
s h e l l s , s i n c e t h e s e a r e l a r g e l y u n a f f e c t e d by t h e s t r u c t u r e in which t h e
atom is embedded.
T h e p h o t o e f f e c t of t h e n e u t r a l atom o r p o s i t i v e ion is u s u a l l y r e f e r r e d
to a s " p h o t o i o n i z a t i o n " , w h e r e a s , in t h e c a s e of a n e g a t i v e ion, one s p e a k s
of " p h o t o d e t a c h m e n t " .
The b a s i c q u a n t i t i e s c h a r a c t e r i z i n g t h e p r o c e s s a r e the d i f f e r e n t i a l
and t h e t o t a l c r o s s - s e c t i o n s . C o n s i d e r i n g a h o m o g e n e o u s flux of m o n o -
e n e r g e t i c photons i m p i n g i n g on t h e a t o m , t h e d i f f e r e n t i a l c r o s s - s e c t i o n da
is d e f i n e d as the r a t i o of t h e p r o b a b i l i t y p e r unit t i m e t h a t the atom a b s o r b s
a photon, t h e r e b y e m i t t i n g an e l e c t r o n in t h e solid angle df2, divided by
t h e d e n s i t y of t h e i n c i d e n t flux (i.e. t h e a v e r a g e n u m b e r of photons c r o s s i n g
t h e unit s u r f a c e , n o r m a l to the d i r e c t i o n of p r o p a g a t i o n , p e r unit t i m e ) .
The total c r o s s - s e c t i o n a is defined s i m i l a r l y , except that the electron is
allowed to be e m i t t e d in any d i r e c t i o n . Obviously, и c a n b e obtained by
i n t e g r a t i n g da o v e r t h e a n g l e s .
679
680 GAVRILA
We s h a l l m a i n l y be c o n c e r n e d with t h e t h e o r e t i c a l d e s c r i p t i o n of the
p r o c e s s . 1 H o w e v e r , i m p o r t a n t p r o g r e s s h a s l a t e l y b e e n m a d e on the e x p e r i -
m e n t a l s i d e . F o r a d i s c u s s i o n of t h i s , s e e the r e f e r e n c e s [ 4 , 6 , 1 1 , 1 3 ] .
A c c o r d i n g to t h e E i n s t e i n equation, f o r photoionization to t a k e p l a c e
t h e condition hu > I m u s t be s a t i s f i e d . C o n s e q u e n t l y , the s t r o n g e r the
b i n d i n g of t h e e l e c t r o n in t h e a t o m , the l a r g e r t h e m i n i m u m e n e r g y of t h e
photons r e q u i r e d to p r o d u c e t h e p r o c e s s . W h e r e a s f o r t h e o u t e r e l e c t r o n s
of light a t o m s only a few eV photons a r e n e e d e d , in the c a s e of t h e i n n e r
s h e l l s of h e a v y a t o m s as m u c h as 80 k e V c a n be n e e d e d . F r o m the q u a n t u m -
m e c h a n i c a l point of view, t h i s shows t h a t in t h e c a s e of light a t o m s and low
photon e n e r g i e s , one c a n do a n o n - r e l a t i v i s t i c c a l c u l a t i o n to d e t e r m i n e t h e
c r o s s - s e c t i o n s , but t h a t , f o r h e a v y a t o m s and h i g h - e n e r g y p h o t o n s , r e l a t i v i t y
m u s t be t a k e n into a c c o u n t .
B e s i d e s t h e o r d i n a r y photoionization p r o c e s s (one photon a b s o r b e d
and one e l e c t r o n e m i t t e d ) , h i g h e r - o r d e r photoionization p r o c e s s e s h a v e
r e c e n t l y b e e n s t u d i e d e x p e r i m e n t a l l y and t h e o r e t i c a l l y . With t h e advent
of i n t e n s e l a s e r b e a m s , it h a s b e e n p o s s i b l e to o b s e r v e t h e p r o c e s s of
" m u l t i - p h o t o n ionization", by which s e v e r a l photons a r e a b s o r b e d in a s i n g l e
e l e m e n t a r y act and one e l e c t r o n is e m i t t e d . F u r t h e r , it h a s b e e n p o s s i b l e
to s t u d y the c a s e of " m u l t i p l e photoionization", by which one photon i s
a b s o r b e d by a c o m p l e x atom and s e v e r a l e l e c t r o n s a r e e m i t t e d . H o w e v e r ,
none of t h e s e d e v e l o p m e n t s will be d i s c u s s e d h e r e .
1. GENERAL LOW-ENERGY FORMULAS
F o r low e n e r g i e s of the e m i t t e d p h o t o e l e c t r o n s and f o r s u f f i c i e n t l y low

v a l u e s of the a t o m i c c h a r g e Z , a n o n r e l a t i v i s t i c c a l c u l a t i o n can be c a r r i e d o u t .
Since d y n a m i c a l l y the e f f e c t of spin i s of r e l a t i v i s t i c o r i g i n and s m a l l , we
s h a l l i g n o r e i t s c o n t r i b u t i o n to the H a m i l t o n i a n . F o r an a t o m with (N + l )
e l e c t r o n s , it h a s the f o r m
N+l
the c o r r e s p o n d i n g e i g e n v a l u e equation b e i n g
Htfz(x) = E<//(x) (1.2)
We d e n o t e by x H = r a , o a the p o s i t i o n on the spin c o - o r d i n a t e s of t h e individual

e l e c t r o n s (cra = ±1) and ф(х) = ф{хг ... x N + 1 ). We s h a l l , h o w e v e r , take into
a c c o u n t spin k i n e m a t i c a l l y , by r e q u i r i n g the a n t i s y m m e t r y of the e i g e n -
f u n c t i o n s ф(х).
U n d e r t h e i n f l u e n c e of a quantized r a d i a t i o n field the a t o m c a n a b s o r b
p h o t o n s , being l e f t in an e x c i t e d o r ionized s t a t e . If the i n t e n s i t y of the
r a d i a t i o n is not too high, one can apply p e r t u r b a t i o n c a l c u l a t i o n with r e s p e c t
to the field in o r d e r to d e t e r m i n e the t r a n s i t i o n a m p l i t u d e of the a t o m f r o m
the i n i t i a l to the f i n a l s t a t e . We shall be i n t e r e s t e d in the a b s o r p t i o n of a
photon of m o m e n t u m flic, e n e r g y e = ficic and p o l a r i z a t i o n v e c t o r
1
The following (general theory, photoionization of one-electron and two-electron atoms) represents
the first part of the lectures given by the author at the Winter College. Part II contained the discussion of
the many-electron atom case and of the relativistic case. For the former, see Refs [4, 8, 9], for the latter [12].
IAEA-SMR-12/26,27 681
L e t I^Í(X) be t h e e n e r g y e i g e n f u n c t i o n d e s c r i b i n g the i n i t i a l s t a t e of t h e
a t o m , of e n e r g y E j . It i s s u p p o s e d to be n o r m a l i z e d to u n i t y a c c o r d i n g to
| ^ ( х ) | 2 dx = 1 (1.3)
H e r e and in the f o l l o w i n g , t h e n o t a t i o n / . . . d x m e a n s i n t e g r a t i o n o v e r the

v a r i a b l e s ? j , . . . . r N j - 1 and s u m m a t i o n o v e r t h e s p i n v a r i a b l e s a 1 ; . . . ctn+j.
We s h a l l d e n o t e by ÊKmsHxi ••• x N+l) energy eigenfunction describing
the f i n a l i o n i z e d s t a t e of t h e a t o m . E r e p r e s e n t s t h e t o t a l e n e r g y of the
a t o m , fiK i s the a s y m p t o t i c m o m e n t u m of the e j e c t e d e l e c t r o n , m s i s the
p r o j e c t i o n of i t s s p i n on t h e z - a x i s (m s = ± 1 / 2 ) and Г s t a n d s f o r t h e q u a n t u m
n u m b e r s of the f i n a l a t o m i c c o r e of e n e r g y E r . One h a s
ft2K2
E = E r + —^— (1.4)
2ß
We s h a l l a s s u m e t h a t r i s n o r m a l i z e d p e r e n e r g y i n t e r v a l and e l e m e n t
of s o l i d a n g l e , i . e .
(x)*//- (x)dx = 6 ( E - E ' ) 5 ( S - n ' ) (1.5)
J EKms Г Ь К ms Г
where n = К/К.
T h e e n e r g y E of t h e f i n a l s t a t e i s f i x e d by t h e e n e r g y c o n s e r v a t i o n
equation E = E j + hex (1.6)
P r o m E q . ( 1 . 4 ) , and with I = E r - E ; , the i o n i z a t i o n p o t e n t i a l of the e j e c t e d
electron, Eq.(1.6), becomes
fi2K2
I + V ^ = ficK . (1.7)
which is the E i n s t e i n equation.

F o r r N + 1 -> со, t h e a s y m p t o t i c b e h a v i o u r of t h e f i n a l s t a t e w a v e f u n c t i o n
i// E i ? m s r (x) should be of t h e f o r m
f hKjU ^ -v —r
ÊKmsr<xl"" X
N+1> =
\ v (2 7 rfi)3j ex
P(iKrN+l)5msK+l^r(xl-"xN) f1-8)
a r e
where o n e - e l e c t r o n s p i n e i g e n v e c t o r s and фг ( x j ... x N ) i s
the a n t i s y m m e t r i c wave f u n c t i o n of the a t o m i c c o r e . T h e n u m e r i c a l c o e f f i c i e n t
in E q . ( 1 . 8 ) was i n t r o d u c e d s o a s to e n s u r e n o r m a l i z a t i o n of the a s y m p t o t i c
s t a t e a c c o r d i n g to E q . ( 1 . 5 ) .
E q u a t i o n (1.8), h o w e v e r , d o e s n o t d e f i n e u n i q u e l y t h e f i n a l s t a t e e i g e n -
f u n c t i o n ÊÏ?msг ( x ) ' T h i s i s a l r e a d y a p p a r e n t in t h e j s i m p l e r c a s e of a
h y d r o g e n - l i k e a t o m . The a s y m p t o t i c b e h a v i o u r e i k r Ç m s ( a ) of t h e e i g e n -
f u n c t i o n ф E | m s ( r ) should be a s s o c i a t e d with s p h e r i c a l outgoing w a v e s e i k r / r ,
o r s p h e r i c a l i n c o m i n g w a v e s e " i k r / r , o r a l i n e a r c o m b i n a t i o n of t h e m .
W h i c h of t h e s e p o s s i b i l i t i e s i s the a s y m p t o t i c b e h a v i o u r c o r r e s p o n d i n g to
our problem?
T h e a n s w e r i s c o n n e c t e d with the d e r i v a t i o n of t h e t r a n s i t i o n a m p l i t u d e
c o r r e s p o n d i n g to p h o t o i o n i z a t i o n . The s a f e s t way of r e a s o n i n g i s to r e l y on
682 GAVRILA
the wave p a c k e t d e s c r i p t i o n of the p r o c e s s . One should f o r m a wave p a c k e t

ф(х, t) which, in the r e m o t e p a s t , coincided with the i n i t i a l s t a t i o n a r y s t a t e
of t h e a t o m ф1 ( x ) e x p ( - i E i t / f t ) . U n d e r t h e i n f l u e n c e of the p e r t u r b i n g r a d i a t i o n
f i e l d , the wave p a c k e t will a l t e r i t s f o r m in t i m e , h o w e v e r i t s evolution i s
u n i q u e l y d e f i n e d by t h e t i m e - d e p e n d e n t S c h r ö d i n g e r e q u a t i o n . We a r e
i n t e r e s t e d in the p r o b a b i l i t y of f i n d i n g , in the r e m o t e f u t u r e , t h e s y s t e m
in a s t a t e d e s c r i b e d by a wave p a c k e t W ( x , t ) , which i s a s u p e r p o s i t i o n of
a s y m p t o t i c s t a t e s E q . ( 1 . 8 ) . T h e s e a r e e i g e n f u n c t i o n s of the e n e r g y o p e r a t o r
K , obtained f r o m H in E q . ( l . l ) by n e g l e c t i n g the i n t e r a c t i o n of t h e outgoing
e l e c t r o n and the a t o m i c c o r e V (i.e. К = H - V ) . The t r a n s i t i o n a m p l i t u d e
we a r e l o o k i n g f o r , i s given by
l i m < W(x,t)|<//(x,t)>
t-»oo
It can be shown t h a t in the m o n o e n e r g e t i c l i m i t f o r the p a c k e t W ( x , t )

and to f i r s t o r d e r in the p e r t u r b i n g r a d i a t i o n f i e l d , the t r a n s i t i o n a m p l i t u d e
i s given by the m a t r i x e l e m e n t
N+1
M = ф(-1* (x){ ) eiKrasPa U ( x ) d x (1.9)
E!?m«r
a- 1
w h e r e s e ' " i s t h e wave f u n c t i o n of the photon, r e t a r d a t i o n i n c l u d e d , and

ф^'Х i s d e f i n e d by
EKmsr
<//("i = 1 + ^ .- ( H - E ) •й&а.Г (UO)
ЕКгпс г L E - H - 16
д
Н е г е ФEJ?msг a n t i s y m m e t r i z e d f o r m of the f u n c t i o n in E q . ( 1 . 8 ) . A f o r m a l
proof of t h i s r e s u l t w a s given by S. A l t s h u l e r (Nuovo C i m e n t o (1956) 246).
In the cas'e of a h y d r o g e n - l i k e a t o m , E q . ( l . l O ) i m p l i e s the f o l l o w i n g
asymptotic behaviour
• ř ň . - G S g . ) ' ^ ' © ^ )
C o n f i r m i n g q u a l i t a t i v e r e a s o n s f o r the u s e of f i n a l - s t a t e wave f u n c t i o n s ,
b e h a v i n g a s y m p t o t i c a l l y like E q . ( l . l l ) , have b e e n given by G. B r e i t and
H. B e t h e ( P h y s . R e v . 93 (1954) 888). An a l t e r n a t i v e proof f o r the c a s e of
b r e m s s t r a h l u n g c a n be found in R e f . I l ] , § 2 9 . 1 .
The s i t u a t i o n i s m o r e c o m p l i c a t e d in the c a s e of a m a n y - e l e c t r o n a t o m ,
w h e r e f r o m E q . ( l . l O ) we get an a s y m p t o t i c b e h a v i o u r which h a s i n c o m i n g
s p h e r i c a l w a v e s in a l l "open c h a n n e l s " . In t h i s c a s e
ÊKmsr(XI' X
N+1> *r- ( X
1'- VVm'^N+l' (1Л2)
r,m
where s
Фг'т'< х Н + 1> ~ ( i S p ) 6
ГГ'6т,т;
exp(-iRrTN+l)
+ (1.13)
f r ' m J ^ N + l ' aN+l^ r.
N+1
IAEA-SMR-12/50 683
F o r all Г ' one should have /
- ^ - Г - ^ Ч Г
T h e s u m o v e r Г' in Eq.(1.12) should be extended o v e r all "open c h a n n e l s " ,

t h a t i s , t h o s e f o r which K r . t u r n s out to be r e a l f r o m E q . ( 1 . 1 4 ) . F o r " c l o s e d
c h a n n e l s " Г ' , when K r - i s i m a g i n a r y , the e x p o n e n t i a l l y d e c r e a s i n g a s y m p t o t i c
b e h a v i o u r should be c h o s e n and t h e r e b y t h e s e t e r m s will not c o n t r i b u t e to
Eq.(1.12).
The a s y m p t o t i c b e h a v i o u r given by E q s (1.12) (1.13) holds only if the
a v e r a g e p o t e n t i a l of the a t o m i c c o r e acting on t h e e j e c t e d e l e c t r o n i s of
s h o r t r a n g e . T h i s i s the c a s e of " p h o t o d e t a c h m e n t " in which, by d e f i n i t i o n ,
we have a n e u t r a l a t o m in the f i n a l s t a t e . If, h o w e v e r , we have a n e u t r a l
a t o m o r a p o s i t i v e ion in t h e i n i t i a l s t a t e , the e j e c t e d e l e c t r o n will m o v e
a s y m p t o t i c a l l y in a C o u l o m b f i e l d . In this c a s e one h a s to i n c l u d e t h e
l o g a r i t h m i c d i s t o r t i o n of the p h a s e s c a u s e d by the C o u l o m b f i e l d in t h e
a s y m p t o t i c b e h a v i o u r of E q . ( 1 . 1 3 ) .
T h e r e i s a c l o s e c o n n e c t i o n b e t w e e n the f i n a l - s t a t e wave f u n c t i o n
Ê^m r ^ ^ y r a p t o t i e b e h a v i o u r of E q s (1.12), (1.13) and the wave f u n c t i o n
^ Ш т г u s e d i n s c a t t e r i n g t h e o r y to d e s c r i b e the c o l l i s i o n of an e l e c t r o n
and Ihe a t o m i c c o r e фг{х1,.,. x n ) . Denoting by T t h e t i m e - r e v e r s a l o p e r a t o r
of the s y s t e m we c a n w r i t e (see G o l d b e r g e r and W a t s o n , C o l l i s i o n T h e o r y ,
§2.6):
(//(") = г)Тф (+) _ (1.15)

EKmsr E, - K , - m s , Г ' '
w h e r e r) i s a p h a s e f a c t o r and Г 1 a r e the q u a n t u m n u m b e r s c o r r e s p o n d i n g
to Г by the t r a n s f o r m a t i o n . E q u a t i o n (1.15) shows t h a t one can u s e f o r the
c a l c u l a t i o n of the p h o t o e f f e c t m a t r i x e l e m e n t (1.9) the wave f u n c t i o n s a l r e a d y
obtained in s c a t t e r i n g t h e o r y .
The d i f f e r e n t i a l c r o s s - s e c t i o n of the photoionization p r o c e s s can be
defined a s t h e p r o b a b i l i t y t h a t , p e r unit t i m e , an e l e c t r o n of a s y m p t o t i c
m o m e n t u m file i s e m i t t e d by the a t o m in the e l e m e n t of solid angle di2,
divided by the d e n s i t y of the i n c o m i n g flux of photons (the a v e r a g e n u m b e r
of photons p e r unit a r e a , n o r m a l to the i n c i d e n t f l u x , and p e r unit t i m e ) .
With M d e f i n e d by E q s (1.9) and (1.5) we find
4ff2e2 i 12
d(jrm = M dň (1.16)
(See a l s o [3] §§59, 69.)

The c o r r e s p o n d i n g t o t a l c r o s s - s e c t i o n can be obtained by i n t e g r a t i n g
Eq.(1.16) o v e r the a n g l e s of the e j e c t e d e l e c t r o n and s u m m i n g o v e r i t s
polarizations ms = ± 1/2:
V
684 GAVRILA
Now, t h e r e i s c o n s i d e r a b l e d e g e n e r a c y a s s o c i a t e d with the e n e r g i e s of

the i n i t i a l s t a t e of the a t o m E j and of the f i n a l a t o m i c c o r e E r . E x p e r i -
m e n t a l l y , it i s u s u a l l y i m p o s s i b l e to d i s t i n g u i s h t r a n s i t i o n s between t h e s e
d e g e n e r a t e s t a t e s . T h e r e f o r e , in o r d e r to c o m p a r e with e x p e r i m e n t ,
E q s (1.16) and (1.17) should be a v e r a g e d o v e r the i n i t i a l s t a t e s i, and
s u m m e d o v e r the f i n a l d e g e n e r a t e s t a t e s Г :
= A > ° rr (1.18)
wZ__,
Г, i
w h e r e w i s the d e g e n e r a c y of the i n i t i a l s t a t e .
An a l t e r n a t i v e way of c a l c u l a t i n g t o t a l c r o s s - s e c t i o n s i s to c o n s i d e r
t h e t r a n s i t i o n of the a t o m f r o m the initial s t a t e ф1 to a f i n a l s t a t e of the
c o n t i n u u m , c h a r a c t e r i z e d by s p e c i f i c q u a n t u m n u m b e r s of the a n g u l a r
m o m e n t a and s p i n s . A s s u m i n g the LS coupling s c h e m e , the s t a t e s of t h e
a t o m i c c o r e can be d e f i n e d by the set of q u a n t u m n u m b e r s T = (a, E T , L T ,
M j , S T , M j ) . The outgoing e l e c t r o n can be c h a r a c t e r i z e d by E k = fi 2 k 2 /2/u;
l , m ; s = 1 / 2 , m s . By coupling the a n g u l a r m o m e n t a of a t o m i c c o r e and
outgoing e l e c t r o n , the s t a t e s of the a t o m can be c h a r a c t e r i z e d by Е = Е т + Е к ;
П = ( a , L , M L , S, M s ) . Supposing that the c o r r e s p o n d i n g f i n a l s t a t e wave
f u n c t i o n i/zgjj (x) i s n o r m a l i z e d p e r e n e r g y i n t e r v a l
ф* (х)ф (x)dx = Ô ( E ' - E ) (1.19)

J Е'П ЕП
t h e c r o s s - s e c t i o n f o r the t r a n s i t i o n i -> E , П i s given by
The m a t r i x e l e m e n t h a s the f o r m
N+l
Мш= fф*п(x) Q V » ^ P a )^(x)dx (1.21)
a=l
A g a i n , by a v e r a g i n g o v e r the i n i t i a l statejs i c o r r e s p o n d i n g to the s a m e e n e r g y
E j and b y s u m m i n g o v e r the f i n a l s t a t e s П of e n e r g y E we get the t o t a l c r o s s -
section
(1.22)
w
П, i
The c r o s s - s e c t i o n s (1.18) and (1.22) r e p r e s e n t the s a m e quantity and

t h e r e f o r e should be e q u a l . T h i s follows r e a d i l y f r o m the f a c t that we have
u s e d in t h e two c a s e s a s f i n a l s t a t e s two d i f f e r e n t e i g e n v e c t o r b a s e s of t h e
s u b s p a c e a s s o c i a t e d with the d e g e n e r a t e eigenvalue E .
When the wave l e n g t h a s s o c i a t e d with the a b s o r b e d photon is m u c h
l a r g e r than the l i n e a r d i m e n s i o n s of the a t o m , the wave f u n c t i o n of the
photon s e Í K l c a n be expanded in m u l t i p o l e s . To l o w e s t o r d e r , in the ( e l e c t r i c )
IAEA-SMR-12/50 685
d i p o l e a p p r o x i m a t i o n , e 1 ^ i s r e p l a c e d by 1 and t h e m a t r i x e l e m e n t s of
E q s (1.9) and (1.21) t a k e the f o r m :
M = (X) ^ 1 P A ^ I ( X ) D X (1.23)
a
C o n s i d e r i n g ф ; (x) and i//En (x) to be e i g e n f u n c t i o n s of t h e t o t a l o r b i t a l and

s p i n a n g u l a r m o m e n t a E. 2 , L z ; S 2 , S z , and b e c a u s e of t h e v e c t o r n a t u r e of
the o p e r a t o r t h e m a t r i x e l e m e n t of E q . ( 1 . 2 3 ) w i l l be n o n z e r o only when
a
s p e c i f i c s e l e c t i o n r u l e s a r e s a t i s f i e d . T h e s e r u l e s a r e A L = 0, ± 1 and
AM L = 0 (if i s t a k e n a l o n g the z - a x i s ) . T h e r e b y the s u m o v e r П in E q . ( 1 . 2 2 )
c o n t a i n s a m a x i m u m of t h r e e t e r m s f o r e a c h i .
It i s c u s t o m a r y to e x p r e s s t h e d i p o l e a p p r o x i m a t i o n of t h e t o t a l c r o s s -
s e c t i o n of E q s (1.20) - (1.22) in a n a l t e r n a t i v e w a y , u s i n g the c o n c e p t of
" o s c i l l a t o r s t r e n g t h " . F o r a t r a n s i t i o n i-»E,Il, which connects the d i s c r e t e
s t a t e i to the c o n t i n u u m s t a t e E , П, one u s e s t h e " d i f f e r e n t i a l o s c i l l a t o r
s t r e n g t h " (or " s p e c t r a l d e n s i t y of o s c i l l a t o r s t r e n g t h s " ) d e f i n e d b y
w h e r e (//En(x) i s s u p p o s e d to be n o r m a l i z e d p e r e n e r g y i n t e r v a l with r e s p e c t
to E , like i n E q . ( 1 . 1 9 ) , and P = 2J Pa. For t r a n s i t i o n s b e t w e e n d e g e n e r a t e
a
i n i t i a l and f i n a l s t a t e s , the d i f f e r e n t i a l o s c i l l a t o r s t r e n g t h c a n be d e f i n e d
b y a v e r a g i n g o v e r the i n i t i a l s t a t e s and s u m m i n g o v e r the f i n a l s t a t e s :
n, í
w h e r e a g a i n w i s the d e g e n e r a c y of t h e i n i t i a l s t a t e .
The t o t a l c r o s s - s e c t i o n s of E q s (1.20) and (1.22) c a n n o w b e w r i t t e n a s
2тг 2 е 2 й df , _
о = v 1.26
ßc dE
with d f / d E g i v e n by E q s (1.24) o r (1.25). T h u s , the two c o n c e p t s : t o t a l

p h o t o i o n i z a t i o n c r o s s - s e c t i o n and d i f f e r e n t i a l o s c i l l a t o r s t r e n g t h a r e
essentially coincident.
E q u a t i o n s (1.24) and (1.25) d e f i n e the " v e l o c i t y " f o r m u l a t i o n of t h e
d i f f e r e n t i a l o s c i l l a t o r s t r e n g t h . H o w e v e r , one c a n f i n d e q u i v a l e n t e x p r e s s i o n s
for this quantity.
Let us abbreviate
R = ^ R A ; P = ; PA; VV = ) VAV (1.27)

a
686 G A VRILA
w h e r e V i s the t o t a l p o t e n t i a l e n e r g y of the H a m i l t o n i a n E q . ( l . l ) :
Ze2 Г1 e2
> (1.28)
« " a < ß r«ß
T h e n , s t a r t i n g f r o m Eq.(1.2) one can e a s i l y p r o v e the f o r m u l a s
' (1-29)
(VV)
Pn-n = n'n d-30)
П n
w h e r e n and n' a r e the q u a n t u m n u m b e r s of two e n e r g y e i g e n f u n c t i o n s .

F u r t h e r , t a k i n g into account the f o r m of V given in Eq.(1.28) we get
VV = Z e 2 ) Ц
3
r
By c o m p a r i n g E q s (1.29) (1.30) with (1.24), we get t h e a l t e r n a t i v e

forms:
d f L _ 2д(Е - E j ]
(1.31)
df A 2ft av
ЕП dZ (1.32)
dE M(E-E,)3
F o r obvious r e a s o n s Eq.(1.31) d e f i n e s the " l e n g t h " f o r m u l a t i o n of the

d i f f e r e n t i a l o s c i l l a t o r s t r e n g t h s , w h e r e a s Eq.(1.32) d e f i n e s the " a c c e l e r a t i o n "
formulation.
All t h r e e f o r m u l a t i o n s , E q s (1.24), (1.31), (1.32), give i d e n t i c a l r e s u l t s
if e x a c t wave f u n c t i o n s ^ and ф ^ a r e u s e d . H o w e v e r , the r e s u l t s d i f f e r
f r o m e a c h o t h e r and f r o m the e x a c t v a l u e when a p p r o x i m a t e wave f u n c t i o n s
a r e u s e d in the c a l c u l a t i o n , a s i s g e n e r a l l y the c a s e . T h i s i s a c o n s e q u e n c e
of the f a c t t h a t in the i n t e g r a l s o c c u r r i n g in E q s (1.24), (1.31), (1.32) d i f f e r e n t
p a r t s of the c o n f i g u r a t i o n s p a c e a r e e m p h a s i z e d in t h e i n t e g r a n d s . T h u s ,
in t h e l e n g t h f o r m u l a t i o n E q . ( 1 . 3 1 ) , it i s t h e l a r g e v a l u e s of t h e c o - o r d i n a t e s
t h a t a r e e m p h a s i z e d , w h e r e a s in the a c c e l e r a t i o n f o r m u l a t i o n Eq.(1.32) it i s
t h e s m a l l v a l u e s which a r e e m p h a s i z e d . On the o t h e r hand, in the v e l o c i t y
f o r m u l a t i o n Eq.(1.24) one f i n d s that the i n t e r m e d i a t e v a l u e s of the c o - o r d i n a t e s
a r e r e l a t i v e l y m o r e i m p o r t a n t . Now, f o r given a p p r o x i m a t e wave f u n c t i o n s
i//;(x) and i// En (x), t h e i r d e g r e e of a c c u r a c y i s not the s a m e t h r o u g h o u t s p a c e ,
which t h u s e x p l a i n s the d i f f e r e n c e in the n u m e r i c a l r e s u l t s obtained f r o m
the different f o r m u l a t i o n s .
In p r a c t i c e the m o s t f r e q u e n t l y u s e d f o r m s of d f / d E a r e the length and
v e l o c i t y f o r m s . It i s h a r d to e s t i m a t e a p r i o r i the r e l a t i v e a c c u r a c y of
t h e two.
T h e a c c e l e r a t i o n f o r m u l a t i o n s e e m s m o r e a p p r o p r i a t e to be u s e d when
s u f f i c i e n t c o r r e l a t i o n is included in the wave f u n c t i o n s and t h e r e f o r e i s not
r e c o m m e n d e d in a p p r o x i m a t i o n s b a s e d on o n e - e l e c t r o n o r b i t a l s . The a g r e e -
m e n t of t h e n u m e r i c a l v a l u e s of at l e a s t two of the f o r m u l a t i o n s f o r d f / d E
IAEA-SMR-12/50 687
(usually l e n g t h and v e l o c i t y ) i s r e g a r d e d a s a t e s t of the a c c u r a c y of t h e s e

v a l u e s and h e n c e of the a c c u r a c y of the a p p r o x i m a t e wave f u n c t i o n s u s e d .
The s p e c t r a l d i s t r i b u t i o n of o s c i l l a t o r s t r e n g t h s can be c h a r a c t e r i z e d
by the v a l u e of i t s m o m e n t s . The m o m e n t of o r d e r r i s d e f i n e d by
Sr = ^ ( Е П - Е ; ) Ч ; + J (E • E . j ' g d E (1.33)
w h e r e I i s the l o w e s t ionization p o t e n t i a l .
Some of the v a l u e s of the m o m e n t s c a n be r e l a t e d to p r o p e r t i e s of the a t o m
in the ground s t a t e , which a r e a c c e s s i b l e to e x p e r i m e n t . The e q u a t i o n s
which follow t h e r e b y a r e denoted by " s u m r u l e s " . (See [3] §61, 62; [4]
§2.5; A. D a l g a r n o , R e v . Mod. P h y s . 35 (1963) 522).
F o r e x a m p l e , we find
S-i = | | (1.34)
s0= N+l (1.35)
Sj = 4 \ i (1.36)
2ц
fi2 92V
S2 (1.37)
9Z2
w h e r e Z , P z , 3 V / 9 Z a r e d e f i n e d by E q . ( 1 . 2 7 ) . Since one d i s p o s e s of r a t h e r
a c c u r a t e g r o u n d - s t a t e wave f u n c t i o n s , the r i g h t - h a n d s i d e s of E q s (1.34) -
(1.37) can be c o n s i d e r e d a s well known. F u r t h e r m o r e , t h e s e q u a n t i t i e s a r e
d i r e c t l y r e l a t e d to e x p e r i m e n t a l p r o p e r t i e s of the a t o m s . One can then c h e c k
if the o s c i l l a t o r s t r e n g t h s d e t e r m i n e d by v a r i o u s m e t h o d s s a t i s f y the s u m
r u l e s . Since all a t o m i c s t a t e s n e n t e r in the d e f i n i t i o n of e a c h S r of E q . ( 1 . 3 3 ) ,
the s u c c e s s of the p r o c e d u r e d e p e n d s on how extended o u r knowledge of the
oscillator strength distribution is.
A n o t h e r m e a n s of c h e c k i n g the a c c u r a c y and c o n s i s t e n c y of t h e r e s u l t s
f o r p h o t o a b s o r p t i o n is to c o m p a r e t h e m with t h o s e obtained f o r i o n i z a t i o n
by e l e c t r o n i m p a c t . When the i n c i d e n t e l e c t r o n i s s u f f i c i e n t l y f a s t (but not
yet r e l a t i v i s t i c ) , the c r o s s - s e c t i o n can be w r i t t e n a s
d*a - ^ p d V d Q ' (1.38)
which c o n t a i n s t h e g e n e r a l i z e d d e n s i t y of o s c i l l a t o r s t r e n g t h s
df(K)_ 2ц ( E - E j ) iKr„
dE ft2 K2 ЕП (1.39)
I '
688 GAVRILA
H e r e К i s the m o m e n t u m t r a n s f e r r e d to the a t o m in the c o l l i s i o n . T h i s i s

the Bethe v e r s i o n of the B o r n a p p r o x i m a t i o n (see Inokuti, R e v . Mod. P h y s . 43
(1971) 297). O b v i o u s l y ,
к -* о
T h e r e f o r e , by e x t r a p o l a t i n g the t h e o r e t i c a l o r e x p e r i m e n t a l r e s u l t s obtained
f o r Eq.(1.39) f r o m E q . ( 1 . 3 8 ) , one can c o m p a r e it with the d a t a f o r p h o t o -
a b s o r p t i o n (an i m p r o v e d p r o c e d u r e i s d e s c r i b e d in [4] §2.6).
2. H Y D R O G E N - L I K E ATOMS
The c a s e of h y d r o g e n - l i k e a t o m s i s the only one in which one c a n d e r i v e

e x a c t a n a l y t i c r e s u l t s f o r t h e p h o t o - i o n i z a t i o n c r o s s - s e c t i o n s . In the following,
we s h a l l outline how one can c a l c u l a t e the m a t r i x e l e m e n t E q . ( 1 . 9 ) , c o r r e s -
ponding to the d i f f e r e n t i a l c r o s s - s e c t i o n , if the a t o m is c o n s i d e r e d to be
i n i t i a l l y in the ground s t a t e I s .
T h e g r o u n d - s t a t e wave f u n c t i o n of t h e a t o m i s
<M?> = ( 0 e Xl
" ' *=t t2-1'
w h e r e ao i s the r a d i u s of t h e f i r s t Bohr o r b i t . The f i n a l , c o n t i n u u m e n e r g y
e i g e n f u n c t i o n of the e l e c t r o n should b e h a v e a s y m p t o t i c a l l y like a plane wave
p l u s a n i n c o m i n g s p h e r i c a l wave ( d i s t o r t e d by t h e C o u l o m b f i e l d ) . Since in
the p r e s e n t c a s e the t i m e r e v e r s a l o p e r a t o r r e d u c e s to c o m p l e x c o n j u g a t i o n ,
Eq.(1.15) m a y b e w r i t t e n
ф('Чг) = (<//«(?))* (2.2)

k -k
T h u s , by i n s e r t i n g f o r the final s t a t e in Eq.(1.9) and t a k i n g into account
E q . ( 2 . 2 ) , we get
M = -ifi j e^s-Vi^dr • (2.3)
The E i n s t e i n c o n s e r v a t i o n equation f o r the p r e s e n t c a s e i s (E; = -й 2 Х 2 /2м,

E k = ft2k2/ 2ц):
k 2 + = { 2 Л )
r ) i s the wave f u n c t i o n which d e s c r i b e s the s c a t t e r i n g of an e l e c t r o n

of a s y m p t o t i c m o m e n t u m fik by an a t o m i c n u c l e u s . It is known to be given
by ([5], C h . X I , §10):
</4>+)(?) = N e 2
V ( l + i Ç ) e i k r E ( - i | , 1; i ( k r - k r ) ) (2.5)
IAEA-SMR-12/50 689
2
w h e r e P is the c o n f l u e n t h y p e r g e o m e t r i c f u n c t i o n , | = Ze2ß/h.2k = Ze /fiv
and N is a n o r m a l i z a t i o n c o n s t a n t . The a s y m p t o t i c b e h a v i o u r of Eq.(2.5) i s
ф® - N 3xp(ikr + § l n ( k r -Ter)) + — exp(ikr - f In k r ) (2.6)

* r->«>
C o m p a r i n g E q s (2.6), (2.2) with E q . ( l . l l ) we s e e t h a t we should take

N = (hkju/^Trfi) 3 ) 1 / 2 .
In o r d e r to i n t e g r a t e the m a t r i x e l e m e n t E q . ( 2 . 3 ) , the following i n t e g r a l
r e p r e s e n t a t i o n f o r F c a n be u s e d :
F ( - i Ç , 1; p) = ~ r e P j ) x H (x - l ) " i £ _ 1 e" p x dx (2.7)
T h e i n t e g r a l o v e r x should be c a r r i e d out along a c l o s e d c o n t o u r in the

c o m p l e x x - p l a n e , e n c i r c l i n g in the c o u n t e r - c l o c k w i s e s e n s e the points 0 and 1.
By i n t r o d u c i n g Eq.(2.7) into Eq.(2.3) and exchanging the o r d e r of i n t e g r a -
t i o n s , one can p e r f o r m the r i n t e g r a t i o n f i r s t . One is then l e f t with the
c l o s e d - c o n t o u r i n t e g r a t i o n o v e r x which c a n be p e r f o r m e d by a p p l i c a t i o n of
the r e s i d u e t h e o r e m . The r e s u l t is
(X - ik) 2 + к2
M - , * e - ï ' r (2 ^ J g ^ p L S i f f i g (2.8)
w h e r e the p r i n c i p a l b r a n c h of the c o m p l e x p o w e r involved should be t a k e n .

( F o r m o r e d e t a i l s on the c a l c u l a t i o n s e e [7] , Ch.VI, § § 4 , 5 . )
L e t u s d e f i n e the r e l a t i v e o r i e n t a t i o n s of the v e c t o r s к, к, s a s shown
in F i g . l . T h e n , by u s i n g the e n e r g y c o n s e r v a t i o n equation (2.4), we have:
(k-;>2+X2 (l-,Scose + ^ ) (2.9)
w h e r e ß = v / c and e = TICK.
I n s e r t i n g Eq.(2.8) into Eq.(2.3), the following i s obtained f o r the d i f f e r e n -
t i a l c r o s s - s e c t i o n Eq.(1.16):
d a = S ? sin2 8 cos2 Ф d n (2Д0)
(^1-/3 cos в + ~ 2 ~ ž J
H e r e S i s the a n g l e - i n d e p e n d e n t quantity:
S_- W z 5 | ( i ± | i ) 2l,
e 2 T ê iSi (2Л1)
1 - e í к5
with
ж < т = a r c t a n , 02 —гтг S 0 (2.12)

k - к 2 - X2
The e x a c t n o n r e l a t i v i s t i c r e s u l t Eq.(2.10) is due to F i s c h e r and Sauter (1931).

690 G A VRILA
FIG. 1. Relative orientation of the vectors к, к, s for photo-ionization by a hydrogenic atom.
The c r o s s - s e c t i o n Eq.(2.10) contains q u a n t i t i e s which a r e of the o r d e r

of the r e l a t i v i s t i c c o r r e c t i o n s and t h e r e f o r e should be d i s c a r d e d , s i n c e we
p e r f o r m e d a n o n r e l a t i v i s t i c c a l c u l a t i o n b a s e d on the S c h r ö d i n g e r H a m i l t o n i a n
E q . ( l . l ) . T h u s , f r o m E q . ( 2 . 4 ) , we get
[ß 2 + (aZ) 2 ]
N e g l e c t i n g 6(132) and 0 ( a 2 Z 2 ) with r e s p e c t to 1, a s r e l a t i v i s t i c c o r r e c t i o n s ,

i t f o l l o w s f r o m E q . (2.10)
do = S sin 2 0 cos 2 cp(l +4/3 cos 0) dfi (2.13)
which r e p r e s e n t s the a n g u l a r d i s t r i b u t i o n o r i g i n a l l y d e r i v e d by S o m m e r f e l d
and Schur (1930). E q u a t i o n (2.13) c o n t a i n s t h e p h y s i c a l l y m e a n i n g f u l p a r t
of E q . ( 2 . 1 0 ) . The f i r s t t e r m r e p r e s e n t s the dipole a p p r o x i m a t i o n of the
m a t r i x e l e m e n t E q . ( 2 . 3 ) , the n e x t t e r m i s the f i r s t - o r d e r c o r r e c t i o n due
to r e t a r d a t i o n .
At low photon e n e r g i e s the second t e r m of Eq.(2.13) i s s m a l l and
t h e r e f o r e dcr/dfi i s p r o p o r t i o n a l to sin 2 6. T h i s shows that f o r any fixed <p,
t h e p h o t o e l e c t r o n s a r e p r i m a r i l y e j e c t e d p e r p e n d i c u l a r l y to the d i r e c t i o n
of the i n c o m i n g p h o t o n s . When the photon e n e r g y i n c r e a s e s and the s e c o n d
t e r m in Eq.(2.13) b e c o m e s a p p r e c i a b l e , the m ax im u m of t h e 6 a n g u l a r
d i s t r i b u t i o n i s s h i f t e d in t h e f o r w a r d d i r e c t i o n . One f i n d s t h a t
0 max
691
IAEA-SMR-12/50
The t o t a l c r o s s - s e c t i o n can be obtained f r o m E q . ( 1 . 1 7 ) . Inserting

Eq.(2.13) we find
47Г
(2.14)
Note that the s e c o n d t e r m of Eq.(2.13) gives no c o n t r i b u t i o n . T h e r e f o r e

Eq.(2.14) c o i n c i d e s with the dipole a p p r o x i m a t i o n r e s u l t (if к 2 i s n e g l e c t e d
with r e s p e c t to X2 in Eq.(2.12)). E q u a t i o n (2.14) i s known a s the Stobbe
c r o s s - s e c t i o n f o r the I s s t a t e .
L e t us now c o n s i d e r the e n e r g y d e p e n d e n c e of the t o t a l c r o s s - s e c t i o n .
One c a n show that at the i o n i z a t i o n t h r e s h o l d (k-*0), a h a s a f i n i t e v a l u e and
i s p r o p o r t i o n a l to Z" 1 0 / 3 == Z~ 3 . H e r e a(v) i s a m o n o t o n i c a l l y d e c r e a s i n g
f u n c t i o n of the f r e q u e n c y v of the i n c o m i n g photon. F o r v a l u e s of v n e a r
the i o n i z a t i o n t h r e s h o l d , a d e c l i n e s as v' 8 ? 3 , then it d e c r e a s e s f a s t e r , until,
f i n a l l y , f o r l a r g e v it b e h a v e s a s y m p t o t i c a l l y l i k e V7/2. ( T h i s r e s u l t i s no
l o n g e r t r u e f o r r e l a t i v i s t i c f r e q u e n c i e s ; in t h i s c a s e the d e c l i n e of ст is
only a s l / y . ) The v a r i a t i o n of a is r e p r e s e n t e d in Fig.(2).
The t o t a l c r o s s - s e c t i o n Eq.(2.14) can be d e r i v e d in an a l t e r n a t i v e w a y .
The wave f u n c t i o n Eq.(2.5) a d m i t s t h e following p a r t i a l wave e x p a n s i o n
([5] , Ch.XI, §10, Eq.(46))
^ ( r ) =N ^ (2Jt + 1) i { e i o £ Ff
k
(
^ r ) P t (cos 9)
i =o
+í
= 4,rti£ £ iV« Y í m ( ř ) Y*m (k) (2.15)
i = 0 m=-{
w h e r e 9 i s the angle between E and г , ст£ = a r g T ( í + 1 - i f ) , and the a s y m p t o t i c
b e h a v i o u r of F c i s d e f i n e d by
Fj(kr) ~ sin ( k r - + ?ln2kr +ae ) (2.16)
I n s e r t i n g Eq.(2.15) into Eq.(2.3) one g e t s

^ t
M =
ß I Z iVo í Y
L(£)Mta.i (2 17
- >
i = 0 m = -J
with
Mtaii = f (RE((r)yim(ř))*e%.P)^ňd? (2.18)
and REJ = 4 7 r N F £ / k r . It can be shown t h a t R ES thus d e f i n e d i s n o r m a l i z e d

per energy interval.
F u r t h e r , one c a n r e a d i l y c h e c k the e q u a l i t y :
2
/|M ü | dn = £ |м{тЛ|2 (2.19)
{m
692 GAVRILA
WAVE NUMBER 1cm"1)
WAVELENGTH IA )
FIG. 2 . The computed photo-ionization cross-section curve for atomic hydrogen. Ф denotes the experimental
value of Benyon and Cairns; from [ 2 ] .
T a k i n g into a c c o u n t a l s o E q s (2.3), (2.15) one f i n d s
47T 2 e 2 fi 2 XT' l „ 12 ,„ „„.

(2.20)
í.m
which i s e x a c t l y what t h e g e n e r a l f o r m u l a Eq.(1.22) b e c o m e s in o u r c a s e .
L e t u s c o n s i d e r now the dipole a p p r o x i m a t i o n , in which e i x r i s r e p l a c e d
by 1. An a r b i t r a r y i n i t i a l s t a t e i will be' c h a r a c t e r i z e d by s o m e q u a n t u m
n u m b e r s n o i 0 m 0 . If we take If along the z - a x i s , b e c a u s e of the s e l e c t i o n
r u l e s i - i 0 ± 1 , m= m 0 , only two n o n v a n i s h i n g t e r m s will r e m a i n in t h e s u m
of Eq.(2.20). On the o t h e r h a n d , the r a d i a l f u n c t i o n s R £ { (r) have i n t e g r a l
r e p r e s e n t a t i o n s s i m i l a r to E q . ( 2 . 7 ) . One can t h e r e f o r e c a l c u l a t e the m a t r i x
e l e m e n t s M i | ) ± mo . £olr,o in a s i m i l a r way a s was done f o r Eq.(2.3) and one
c a n t h u s r e d e r i v e the t o t a l c r o s s - s e c t i o n a obtained in Eq.(2.14),
D i f f e r e n t i a l and t o t a l c r o s s - s e c t i o n s s i m i l a r to E q s (2.10), (2.13),
and (2.14) f o r t h e I s i n i t i a l s t a t e , have b e e n d e r i v e d a l s o f o r the 2s, 2p
s t a t e s (see [7] , Ch. VI, §6, and [3], §710). It i s p o s s i b l e to give g e n e r a l
a n a l y t i c e x p r e s s i o n s f o r the m a t r i x e l e m e n t s of photoionization f r o m any n i
s t a t e , even i n c l u d i n g r e t a r d a t i o n (see W . G o r d o n , Ann. P h y s . ( P a r i s ) 5
(1929) 1051 and J . F i s c h e r , Ann. P h y s . (Leipzig) П_ (1931) 489). H o w e v e r ,
t h e f o r m u l a s b e c o m e i n c r e a s i n g l y c u m b e r s o m e f o r h i g h e r n so t h a t one h a s
t r i e d to d e r i v e a p p r o x i m a t e e x p r e s s i o n s f r o m . t h e m . T h u s , the t o t a l c r o s s -
IAEA-SMR-12/50 693
s e c t i o n p e r e l e c t r o n in the n - t h i n i t i a l s t a t e ( a v e r a g e d o v e r t h e Í s u b s t a t e s )
h a s b e e n w r i t t e n in t h e f o r m
w h e r e a = e 2 / f i c and g i s the so c a l l e d " G a u n t f a c t o r " } E q . ( 2 . 2 1 ) with g = 1

w a s f i r s t o b t a i n e d by K r a m e r s u s i n g old q u a n t u m t h e o r y (1923). The f a c t o r
g h a s b e e n e v a l u a t e d n u m e r i c a l l y f o r s e v e r a l n and c e r t a i n r a n g e s of p h o t o n
e n e r g i e s . It t u r n s out t h a t g i s r a t h e r c l o s e to u n i t y . A n a l y t i c a s y m p t o t i c
e x p a n s i o n s h a v e b e e n g i v e n f o r it ( s e e [6], § 3 . 4 ; H. G r i e m , P l a s m a S p e c t r o -
s c o p y §5.3 and the r e f e r e n c e s q u o t e d t h e r e i n ) . E q u a t i o n (2.21) i s f r e q u e n t l y
u s e d in a s t r o p h y s i c s .
U n t i l now o n l y one a t t e m p t h a s b e e n m a d e to m e a s u r e t h e p h o t o i o n i z a t i o n
of h y d r o g e n d i r e c t l y (Benyon, 1965; B e n y o n and C a i r n s , 1966). T h e t o t a l
c r o s s - s e c t i o n m e a s u r e m e n t w a s in v e r y good a g r e e m e n t with t h e o r y (see
Pig.2). However, c r i t i c i s m has been e x p r e s s e d that the a g r e e m e n t was
r a t h e r f o r t u i t o u s and t h a t t h e r e f o r e t h e e x p e r i m e n t could not be c o n s i d e r e d
a s c o n c l u s i v e ( s e e [2], § 2 . 2 ) .
3. T W O - E L E C T R O N ATOMS
T h e c a s e of t w o - e l e c t r o n a t o m s i s s t i l l s u f f i c i e n t l y s i m p l e so t h a t r a t h e r
r e f i n e d n u m e r i c a l c a l c u l a t i o n s could be m a d e f o r t h e p h o t o i o n i z a t i o n
c r o s s - s e c t i o n s . B e s i d e s , in t h i s c a s e one c a n m o r e e a s i l y d e s c r i b e the
c u m b e r s o m e m e t h o d s u s e d f o r c o m p l e x a t o m s , to be c o n s i d e r e d l a t e r .
We s h a l l t h e r e f o r e d i s c u s s t h e t w o - e l e c t r o n a t o m in s o m e d e t a i l .
T w o - e l e c t r o n a t o m s a r e s u c h a s n e u t r a l H e , t h e p o s i t i v e i o n s of L i + ,
e t c . , and the n e g a t i v e h y d r o g e n i o n H " . H" i s a l o o s e l y bound s t r u c t u r e
(0.7 5 eV d i s s o c i a t i o n e n e r g y i n t o a H a t о т p l u s o n e e l e c t r o n ) w h i c h h a s
b e e n s t u d i e d e x t e n s i v e l y . It h a s b e e n found t o b e an i m p o r t a n t f a c t o r in c o n -
n e c t i o n with t h e o p a c i t y of t h e a t m o s p h e r e s of t h e s u n and s i m i l a r s t a r s .
In t h e a p p r o x i m a t i o n d e f i n e d by E q . ( l . l ) , in which s p i n - d e p e n d e n t
f o r c e s a r e n e g l e c t e d , t h e t o t a l s p i n a n g u l a r m o m e n t u m § = i§i + § 2 of the
two e l e c t r o n s o b v i o u s l y c o m m u t e s with t h e H a m i l t o n i a n . H e n c e t h e r e e x i s t s
a c o m p l e t e s e t of e i g e n f u n c t i o n s c o m m o n to H, Š 2 , S z . T h e e i g e n v a l u e s
of S 2 , S z a r e s ( s + l ) f i 2 and m s R, w h e r e s = 0, m s = 0 and s = 1, m s = 0 , ± 1.
The c o r r e s p o n d i n g eigenfunctions have well-defined s y m m e t r y p r o p e r t i e s
with r e s p e c t to t h e s p i n v a r i a b l e s of the two e l e c t r o n s . T h e y a r e s y m m e t r i c
in the c a s e s = 1, m s = 0, ± 1 ( t r i p l e t s t a t e s ) and a n t i s y m m e t r i c f o r s = 0,
m s =0 ( s i n g l e t s t a t e ) . Since t h e t o t a l e n e r g y e i g e n f u n c t i o n s <//(х 1 ( х 2 ) s h o u l d
be a n t i s y m m e t r i c with r e s p e c t to t h e i n t e r c h a n g e of t h e s p a t i a l and s p i n
c o - o r d i n a t e s of t h e two e l e c t r o n s , it f o l l o w s t h a t t h e e i g e n f u n c t i o n s c a n be
c h o s e n a s p r o d u c t s of f u n c t i o n s of t h e s p a c e c o - o r d i n a t e s and of the a f o r e -
m e n t i o n e d s p i n wave f u n c t i o n s . T h e n , the s p a c e f u n c t i o n m u l t i p l y i n g the
s i n g l e t s p i n s t a t e s h o u l d be s y m m e t r i c , w h e r e a s t h e f u n c t i o n s m u l t i p l y i n g
the t r i p l e t s p i n s t a t e s s h o u l d be a n t i s y m m e t r i c :
ф+(г1,г2) = ф+(г2,г1), singlet case

- - (ЗЛ>
ф ( r 1 ( r 2 ) = -ф ( r 2 , r j ) , triplet case
694 GAVRILA
T h e f a c t t h a t the s p i n d e p e n d e n c e of t h e e n e r g y e i g e n f u n c t i o n s f a c t o r s out
i s c h a r a c t e r i s t i c o n l y of t w o - e l e c t r o n s y s t e m s and r e p r e s e n t s a c o n s i d e r a b l e
s i m p l i f i c a t i o n in c a l c u l a t i o n s . T h u s , t h e m a t r i x e l e m e n t of a n y o p e r a t o r ,
s y m m e t r i c in t h e s p a t i a l c o - o r d i n a t e s of the two e l e c t r o n s (like t h e o n e s
o c c u r r i n g in E q s (1.9), (1.23)), will be z e r o u n l e s s it c o n n e c t s s t a t e s of
t h e s a m e t y p e of s p a t i a l s y m m e t r y . T h i s e x p l a i n s why t h e l e v e l s of t w o -
e l e c t r o n a t o m s f a l l i n t o two d i s t i n c t s y s t e m s ( s i n g l e t and t r i p l e t ) w h i c h do
not c o m b i n e o p t i c a l l y with e a c h o t h e r .
The ground state is s y m m e t r i c with r e s p e c t to the spatial c o - o r d i n a t e s
( ( I s ) 2 c o n f i g u r a t i o n ) and i s a s i n g l e t . It c a n be c o m b i n e d o p t i c a l l y o n l y with
s i n g l e t s t a t e s . B e s i d e s , it h a s q u a n t u m n u m b e r s L = M L = 0. C o n s e q u e n t l y ,
t h e q u a n t u m n u m b e r s of t h e f i n a l s t a t e s h o u l d be L = 1, M L = 0 i n o r d e r
t h a t t h e d i p o l e a p p r o x i m a t i o n m a t r i x e l e m e n t in E q s (1.23) d o e s not v a n i s h
(we n o w c o n s i d e r t h e p o l a r i z a t i o n v e c t o r s to be d i r e c t e d a l o n g t h e z - a x i s ) .
T h e t o t a l c r o s s - s e c t i o n E q . ( 1 . 2 2 ) will be g i v e n by t h e c o n t r i b u t i o n of t h i s
s i n g l e t e r m . It c a n b e w r i t t e n in the f o r m of E q . ( 1 . 2 6 ) w h e r e in t h e p r e s e n t
c a s e t h e d i f f e r e n t i a l o s c i l l a t o r s t r e n g t h in t h e v e l o c i t y f o r m u l a t i o n i s g i v e n b y
df v = 2
dE ftc/uK II K U , M ^ i . +
.
dr„ (3.2)
M o s t of t h e w o r k w h i c h h a s b e e n done r e f e r s to the c a l c u l a t i o n of t o t a l c r o s s -
sections, Eq.(3.2).
T h e g r o u n d - s t a t e wave f u n c t i o n s of t w o - e l e c t r o n a t o m s h a v e b e e n
c a l c u l a t e d with a r a t h e r high d e g r e e of a c c u r a c y b y a p p l y i n g to t h e S c h r ö d i n g e r
e q u a t i o n (1.2) t h e v a r i a t i o n a l m e t h o d . T h i s c o n s i s t s of m i n i m i z i n g t h e
functional
w i t h i n a c e r t a i n t y p e of t r i a l f u n c t i o n s .
In p h o t o i o n i z a t i o n c a l c u l a t i o n s , m o s t f r e q u e n t l y H y l l e r a a s - t y p e t r i a l
functions have been used:
= N i e " a s ^ Xabcsatbuc (3.4)

a, b, с
w h e r e s = r - [ + r 2 , t = r 1 - r 2 , u = | r i - r 2 | and a , X a b c a r e c o n s t a n t p a r a m e t e r s
d e t e r m i n e d b y the v a r i a t i o n a l m e t h o d . In E q . ( 3 , 4 ) , a , b , с a r e i n t e g e r p o w e r s
and b i s e v e n (ф^ s h o u l d be s y m m e t r i c ) ; N; i s t h e n o r m a l i z a t i o n c o n s t a n t .
In t h e c a s e of H" o n e h a s a l s o u s e d S c h w a r z - t y p e v a r i a t i o n a l w a v e
f u n c t i o n s of t h e f o r m
ф,(г1, R 2 ) = N I Е" А(Г1 + Г 2 ) ^ X A B C R? 2 (RÏR£ +rirh2) (3.5)
a, b, с
w h e r e s o m e of t h e p o w e r s i n v o l v e d a r e f r a c t i o n a l .
IAEA-SMR-12/50 695
L e t u s now c o n s i d e r the wave f u n c t i o n f o r the f i n a l s t a t e . Any s y m -

m e t r i c o r a n t i s y m m e t r i c f u n c t i o n ф* r 2 ) c a n be e x p a n d e d in h y d r o g e n - l i k e
e n e r g y e i g e n f u n c t i o n s (which in t h e p r e s e n t c a s e a r e the e i g e n f u n c t i o n s of
t h e a t o m i c c o r e ) ф щ ^ ( r 1 ) = R n < i ( ^ ) Y ^ ( ř j ), a c c o r d i n g to:
=75<1±Р12)Х KbmČtWnlÂ) (3.6)

nlj mj
Here P12 the o p e r a t o r p e r m u t i n g the v a r i a b l e s and r 2 . By expanding

f u r t h e r fn{ m (?2) i' n s p h e r i c a l h a r m o n i c s , one c a n w r i t e
m , ? 2 > = j=2 d ± p u ) X Z F " i m i

; r z ( r 2 ) Y
^ 2 ( í 2 ) ^ i m i ( ? i ) (3.7)
nJ^m^ i2m2
At t h i s point it i s u s e f u l to i n t r o d u c e t h e e i g e n f u n c t i o n s of t h e t o t a l angular
m o m e n t a L 2 , L z , w h i c h we s h a l l d e n o t e by The t h e o r y of t h e a d d i t i o n
of a n g u l a r m o m e n t a y i e l d s t h e e q u a t i o n :
C
^ Ы ^ т Л » =X «TnUm2 i 3 -»)
LM L
w h e r e the s u m m a t i o n i s l i m i t e d by t h e c o n d i t i o n s | Л1 - i 2 I s L š +
£ 2»
- L s M L s L . B y m u l t i p l y i n g E q . ( 3 . 8 ) by R n i ] ( r 1 ) and d e n o t i n g
*nMlLML<?i'ř2> - R ^ l ^ l ř i , ^ ) (3.9)
E q . (3.7) b e c o m e s :
Fnt
tf ( ? , . ? , ) = ^ ( 1 ±P12 )Y I ' V 2 L S ( r 2 > ' * 4 , L M L (?1. ř 2 ) (ЗЛО)
ní,í 2 LM
We have a b b r e v i a t e d h e r e
^níjíj.LS (Г2> =
X С «1т1« 2 т 2 ^níjiri!, i 2 m 2 ( r 2 ) (3.11)
rrij m2
It can be shown t h a t t h e f u n c t i o n s P on the l e f t hand s i d e of E q . ( 3 . 1 1 ) do
not depend on M L and t h e r e f o r e we h a v e o m i t t e d t h i s s u b s c r i p t . The s u b -
s c r i p t S = 0, 1 d e s i g n a t e s the s i n g l e t and t r i p l e t a l t e r n a t i v e s , c o r r e s p o n d i n g
t o ± o n t h e r i g h t - h a n d side of E q . ( 3 . 1 1 ) .
In E q . ( 3 . 1 1 ) t h e o r d e r of the s u m m a t i o n s o v e r v = { n , i2} a n d L , ML
c a n be r e v e r s e d , s o t h a t we c a n w r i t e
^ ( Í L ^ ^ D I P U L ^ M ^ ^ Í . Í ! ) (3.12)
LM^ v
Now, in the p r o b l e m a t h a n d , we a r e i n t e r e s t e d in wave f u n c t i o n s
ÊLM l (^1' ^2) d e s c r i b i n g s t a t e s of s p e c i f i c q u a n t u m n u m b e r s L , M L . In t h i s
c a s e , the s u m o v e r L , M L should be d r o p p e d in E q . ( 3 . 1 2 ) .
696 GAVRILA
In o r d e r that ф ± of Eq.(3.12) be an e n e r g y e i g e n f u n c t i o n of p o s i t i v e
e i g e n v a l u e E of the S c h r ö d i n g e r equation E q . ( 1 . 2 ) , the r a d i a l f u n c t i o n s
F„LS (r 2 ) m u s t s a t i s f y a c e r t a i n s e t of e q u a t i o n s . T h e s e e q u a t i o n s can be obtained
by i n t r o d u c i n g ф±(г i , r 2 ) into the S c h r ö d i n g e r e q u a t i o n , m u l t i p l y i n g the l a t t e r
by (ri» an
d i n t e g r a t i n g o v e r r j and r 2 :
JФ* (г1з ^т-Е)ф±(г1 ,72)dr1dr2 = 0 (3.13)
The a c t u a l d e r i v a t i o n i s s o m e w h a t involved and was c a r r i e d out by P e r c i v a l

and Seaton ( P r o c . C a m b r . P h i l . Soc. 53 (1957) 654). T h e y found
+ k
( S - n ) n L s ( r ) = % Y IV(„. , ' ) L - W ( , . ,-) L S ] F .Jr)
(3.14)
The e x p l i c i t f o r m of the p o t e n t i a l o p e r a t o r s V(v,i/')L and the exchange
o p e r a t o r s W(v, ^')ls i s c o m p l i c a t e d and can be found in the r e f e r e n c e quoted.
The V ' s a r e m u l t i p l i c a t i v e o p e r a t o r s , w h e r e a s the W ' s a r e i n t e g r a l o p e r a t o r s .
One h a s denoted:
k2 = 2M(E-En)/K2
E q u a t i o n s (3.14) have to be i n t e g r a t e d t a k i n g into account adequate

b o u n d a r y c o n d i t i o n s . Suppose that t h e f i n a l s t a t e of the a t o m (i.e. a t o m i c
c o r e plus outgoing e l e c t r o n ) i s c h a r a c t e r i z e d by the q u a n t u m numbers
(v = n , l-y, £ 2 ) , L , M L . F o r the "open c h a n n e l s " ( k 2 > 0), the required
asymptotic behaviour is
{ T
\ z J ^ y - S+w.exp(-i0u.)] (3.15)
w h e r e {S^j,•} i s a s e t of n u m b e r s g e n e r a t i n g the S m a t r i x , and
i27T , (Z - l)e 2 ju . „.
h =knr - 2 + l n 2 k
" r + (3.16)
(3.17)
In the c a s e of He and p o s i t i v e i o n s (Li + , etc.) the p h a s e s of Eq.(3.16)

p r e s e n t l o g a r i t h m i c d i s t o r t i o n s due to the f a c t t h a t the e j e c t e d e l e c t r o n m o v e s
in the C o u l o m b f i e l d of the ionic c o r e . F o r H " , h o w e v e r , Z = 1 and the
l o g a r i t h m i c t e r m s in the p h a s e s v a n i s h , b e c a u s e the e j e c t e d e l e c t r o n m o v e s
in the f i e l d of the n e u t r a l h y d r o g e n a t o m . A s we s h a l l p r e s e n t l y s e e , t h i s
h a s i m p o r t a n t c o n s e q u e n c e s on the e n e r g y d e p e n d e n c e of the c r o s s - s e c t i o n s .
F o r " c l o s e d c h a n n e l s " ( k 2 < 0) the a s y m p t o t i c b e h a v i o u r should be
given by
F ^ (r) ~ Nro.exp к + (3.18)

- 1 > ! й г Iт 1n*п I 2 | к
" 1 | г
In a l l c a s e s , at the o r i g i n F ^ g s ) (0) = 0.
IAEA-SMR-12/50 697
The a s y m p t o t i c b e h a v i o u r Eq.(3.15) e n s u r e s t h a t ф E L M ( ? I > ? 2 ) i s n o r m a l i z e d

L
p e r e n e r g y i n t e r v a l (see E q . ( 1 . 1 9 ) a s r e q u i r e d by E q . ( 3 . 2 ) .
The a s y m p t o t i c b e h a v i o u r Eq.(3.15) should be c o n t r a s t e d to the one
r e q u i r e d f o r the s c a t t e r i n g p r o b l e m :
^ ( r ) ^ ( ^ г ) Ч ^ ' е х р ( ^ О * SyVexp(i0,.)] (3.19)
(the c o n s t a n t fi2)1/2 is i r r e l e v a n t in t h i s c a s e and can be o m i t t e d ) .

O u r E q s (3.14) f o r m an i n f i n i t e s e t of coupled i n t e g r o - d i f f e r e n t i a l
e q u a t i o n s f o r the f u n c t i o n s F v Ls(r). In any p r a c t i c a l c a l c u l a t i o n it is p o s s i b l e
to c o n s i d e r only a f i n i t e n u m b e r of t e r m s in the e x p a n s i o n Eq.(3.12) of
^ e l M l ^ i • ^2) a n c l h e n c e the t r u n c a t e d ф will no l o n g e r s a t i s f y the S c h r ö d i n g e r
e q u a t i o n e x a c t l y . H o w e v e r , it can be shown by the Kohn v a r i a t i o n a l p r i n -
ciple t h a t , if the t r u n c a t e d ф s a t i s f i e s E q . ( 3 . 1 3 ) , and t h e r e f o r e the f u n c t i o n s
Fi/Ls( r ) r e t a i n e d s a t i s f y E q s (3.14), t h e i r p h a s e s h i f t s will have an e r r o r of
second o r d e r in Ьф, the d i f f e r e n c e b e t w e e n the e x a c t and the t r u n c a t e d ф.
T h e r e b y , by solving n u m e r i c a l l y E q s (3.14) f o r the r a d i a l f u n c t i o n s F y L S (r)
one h a s r e t a i n e d , the r e s u l t i s e x p e c t e d to be " b e s t " in t h e v a r i a t i o n a l s e n s e .
We s h a l l now d i s c u s s s o m e of the a c t u a l p h o t o i o n i z a t i o n c a l c u l a t i o n s
c a r r i e d out f o r t w o - e l e c t r o n a t o m s . We s h a l l c o n s i d e r f i r s t the c a s e of He
and p o s i t i v e ions (like Li + ) and t h e n that of H " .
3.1. He and p o s i t i v e i o n s
The l o w e s t p o s s i b l e a p p r o x i m a t i o n f o r the f i n a l s t a t e wave f u n c t i o n

ÊL = 1 M = o(*"l> ^2) within the above s c h e m e c o n s i s t s of r e t a i n i n g a s i n g l e
t e r m in the e x p a n s i o n E q . ( 3 . 1 2 ) . T h i s will have to be the one y i e l d i n g the
a s y m p t o t i c , f i n a l s t a t e of the a t o m : n= 1, i j = 0 , i 2 = L = 1. T h e r e b y we t a k e
F(r2 F ( r 1) .
R
Е, L = L , M = 0 10<rl) - T - " Y
0 0 < r l ) Y10<r2 ) + R l o ( r 2 ) - i r - V Y 00< r 2 ) Y
l0(rl)
F(r2)
N exp(-Zr,) r
c o s 9 2 + e x p ( - Z r 2 ) r— ^ c o s (3.20)
2 1 J
w h e r e F ( r ) is p r o p o r t i o n a l to the f u n c t i o n F ^ g c o r r e s p o n d i n g to the a f o r e -
m e n t i o n e d q u a n t u m n u m b e r s and N i s a c o n s t a n t . F ( r ) will then s a t i s f y a
s i n g l e i n t e g r o - d i f f e r e n t i a l equation of the type (3.14), with no s u m m a t i o n
on i t s r i g h t - h a n d s i d e and with v' r e p l a c e d by v.
A s t i l l c r u d e r a p p r o x i m a t i o n w a s u s e d in the e a r l y c a l c u l a t i o n of
S. Huang ( A s t r o p h y s . J . 108 (1948) 354) who, i n s t e a d of d e t e r m i n i n g v a r i a t i o n -
a l l y F ( r ) , s i m p l y took it to be the c o n t i n u u m r a d i a l f u n c t i o n c o r r e s p o n d i n g
to a C o u l o m b p o t e n t i a l of c h a r g e Z = 1 (the outgoing e l e c t r o n i s m o v i n g at
l a r g e d i s t a n c e s in a C o u l o m b p o t e n t i a l of t h i s c h a r g e ) . The m a t r i x e l e m e n t
w a s then i n t e g r a t e d a n a l y t i c a l l y .
The v a r i a t i o n a l c a l c u l a t i o n of F ( r ) , a c c o r d i n g to E q . ( 3 . 1 4 ) , w a s c a r r i e d
out f o r He and L i + by S t e w a r t and Webb ( P r o c . P h y s . Soc. ^82 (1963) 532).
The g r o u n d - s t a t e wave f u n c t i o n s w e r e t a k e n to be of t h e H y l l e r a a s type
E q . ( 3 . 4 ) with s i x p a r a m e t e r s . The r a n g e of e n e r g i e s of the outgoing e l e c t r o n
c o n s i d e r e d w a s : 0 < E K < 1 2 8 R y . The d i f f e r e n t i a l o s c i l l a t o r s t r e n g t h was
c o m p u t e d in the d i p o l e - l e n g t h , v e l o c i t y , and a c c e l e r a t i o n f o r m u l a t i o n s .
6 9 8 GAVRILA
V 0.1
\v •AUTOION I ZING STATES
V«О \4
0.01
* v \
V
0.001
s4
J L 0.0001
100 200 300
E (eV)
FIG. 3. Helium photo-ionization cross-section according to Fano and Cooper, showing the h i g h - e n e r g y
region including the data of Lukirskii e t al. (О), Samson ( • ) , Lowry et al. ( • ) , together with the theories
of Burke and Mc Vicar ( ), Bell and Kingston ( ), and a hydrogenic approximation ( );
from 12].
The s p r e a d yielded by t h e d i f f e r e n t f o r m u l a t i o n about t h e i r m e a n w a s r a t h e r

l a r g e ( h o w e v e r , not e x c e e d i n g 8%).
A m o r e r e f i n e d c a l c u l a t i o n was c a r r i e d out f o r He by B u r k e and Mc V i c a r
( P r o c . P h y s . Soc. 86 (1965) 989) who included in t h e e x p a n s i o n Eq.(3.12)
not only the s t a t e I s but a l s o the s t a t e s 2 s , 2p. F o r t h e ground s t a t e they
u s e d t h e t w e n t y - p a r a m e t e r H y l l e r a a s - t y p e wave f u n c t i o n of H a r t and H e r z b e r g
(1957). T h e r a n g e of e n e r g i e s c o v e r e d w a s 0 < E K < 2 . 4 Ry. E x c e l l e n t a g r e e -
m e n t was found b e t w e e n the l e n g t h and v e l o c i t y f o r m u l a t i o n s of the d i f f e r e n t i a l
o s c i l l a t o r s t r e n g t h s (see F i g . 3 ) . T o w a r d s the high e n e r g y end of the i n t e r v a l
c o n s i d e r e d , the r e s u l t s obtained lie above t h o s e of S t e w a r t and Webb, d i s -
c l o s i n g the c o n t r i b u t i o n of the e x t r a s t a t e s 2s, 2p included in the c a l c u l a t i o n .
H o w e v e r , the m a i n e m p h a s i s of the work of B u r k e and M c V i c a r l i e s in the
a n a l y s i s of the r e s o n a n c e s o c c u r r i n g in the c r o s s - s e c t i o n below the He
(n = 2) f o r m a t i o n t h r e s h o l d at 65.4 eV.
A d i f f e r e n t a p p r o a c h to m a k e a l l o w a n c e f o r the e f f e c t of p o l a r i z a t i o n
of the a t o m i c c o r e by the e j e c t e d e l e c t r o n was applied to He by B e l l and
K i n g s t o n ( P r o c . P h y s . Soc. 90 (1967) 31). The f i n a l - s t a t e wave f u n c t i o n
w a s t a k e n of t h e f o r m E q . ( 3 . 2 0 ) , h o w e v e r , t h e F ( r ) was d e t e r m i n e d not by
Eq.(3.14) but by t h e m e t h o d of " p o l a r i z e d o r b i t a l s " , d e v e l o p e d f o r the
s c a t t e r i n g p r o b l e m by T e m k i n (see T e m k i n and L a m k i n , P h y s . Rev. 121
(1961) 788). T h e c o n t i n u u m wave f u n c t i o n i s w r i t t e n in the f o r m
0+(?!,?2) (3.21)
IAEA-SMR-12/50 699
о
ш
1Л
о
2
О 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
WAVELENGTH \ (1000 Ä)
FIG. 4. The bound-free H" absorption cross-section calculated using the 70-parameter bound function,
the three forms of the dipole operator (L, V, A), with the continuum ls-2s-2p-3s-3p-3d exchange function.
Experimental values (O) are from Smith and Burch,-normalized at a wavelength of 528 0 Â; from [ 2 ] .
w h e r e f(r 2 ) d e s c r i b e s the outgoing e l e c t r o n and ф0(г1) i s the g r o u n d state^

of H e + . </>Pol(r2 , r j ) r e p r e s e n t s the change of the a t o m i c wave f u n c t i o n at r a
owing to the p r e s e n c e of the outgoing e l e c t r o n at r 2 , which can be d e t e r m i n e d .
T h e equation s a t i s f i e d by f 2 ( r ) can be d e t e r m i n e d by i n t r o d u c i n g Eq.(3.21)
into
(3.22)
(A d e s c r i p t i o n of the i n t e g r o - d i f f e r e n t i a l equation which r e s u l t s and of the

m e t h o d f o r s o l v i n g it can be found in Sloan, P r o c . R. Soc. A 281 (1964)
151). Once f ( r ) i s d e t e r m i n e d , it i s not u s e d in c o n j u n c t i o n with Eq.(3.21),
but i s r a t h e r i n s e r t e d in Eq.(3.20). The i n t e g r a t i o n of the m a t r i x e l e m e n t
w a s c a r r i e d out u s i n g two d i f f e r e n t H y l l e r a a s - t y p e wave f u n c t i o n s (the one
of S t e w a r t and Webb, with s i x p a r a m e t e r s , and the one of H a r t and H e r z b e r g ,
with 20 p a r a m e t e r s ) .
V e r y good a g r e e m e n t was found b e t w e e n the d i p o l e - l e n g t h and v e l o c i t y
f o r m u l a t i o n s . The r e s u l t s showed l i t t l e i m p r o v e m e n t when u s i n g the H a r t
and H e r z b e r g g r o u n d - s t a t e wave f u n c t i o n , o v e r the one of S t e w a r t and Webb.
T h i s shows t h a t the c r i t i c a l i s s u e i s s t i l l the wave f u n c t i o n of the f i n a l s t a t e .
The p o l a r i z e d o r b i t a l f i n a l - s t a t e wave f u n c t i o n m u s t be c o n s i d e r e d s u p e r i o r
to the H a r t r e e - F o c k type of a p p r o x i m a t i o n used by S t e w a r t and Webb. H o w -
e v e r , it i s d i f f i c u l t to judge if it i s b e t t e r than the c l o s e - c o u p l i n g wave f u n c t i o n
of B u r k e and M c V i c a r , b e c a u s e the l a t t e r t a k e s into a c c o u n t s h o r t r a n g e
c o r r e l a t i o n and the e f f e c t of doubly e x c i t e d s t a t e s . Although the d i f f e r e n c e
700 GAVRILA
0 2 4 6 6 10 12 1Л 16
WAVE LENGTH Х(ЮООД)
FIG. 5. The total H" photodetachment cross-section, including the Macek resonance; from [ 2 ] .
in r e s u l t s of the two m e t h o d s i s s m a l l , the c l o s e - c o u p l i n g c a l c u l a t i o n i s

c o n s i d e r e d to be m o r e a c c u r a t e in the low e n e r g y r e g i o n (below 65.4 eV).
T h e p a p e r by B e l l and K i n g s t o n c o n t a i n s a l s o an e x a m p l e of the a p p l i c a t i o n
of the s u m r u l e s E q s (1.34 - 1.36) f o r S_ 1( S Q , S + 1 , to t e s t the a c c u r a c y of
the r e s u l t s .
The t h e o r e t i c a l r e s u l t s obtained a r e c o m p a r e d with the e x p e r i m e n t a l
r e s u l t s in F i g . 3 .
3.2. The c a s e of H"
The a b s o r p t i o n c o e f f i c i e n t due to b o u n d - f r e e t r a n s i t i o n s of H~ h a s b e e n
e x t e n s i v e l y studied by C h a n d r a s e k h a r and his c o l l a b o r a t o r s (1942-1958).
H o w e v e r , the m o s t a c c u r a t e r e s u l t s w e r e obtained by G e l t m a n ( A s t r o p h y s .
J . Ш> (1962) 935) and Doughty, F r a s e r and M c E a c h r a n (Mon. Not. R . A s t r .
Soc. 132 (1966) 255).
In the w o r k of G e l t m a n , two g r o u n d - s t a t e wave f u n c t i o n s w e r e u s e d ,
one of the H y l l e r a a s type Eq.(3.4) with 20 p a r a m e t e r s ( due to H a r t and
H e r z b e r g , 1957) and the o t h e r one of t h e S c h w a r t z t y p e , with 70 p a r a m e t e r s .
F o r t h e c o n t i n u u m s t a t e a highly c o r r e l a t e d wave f u n c t i o n was u s e d , the
c o e f f i c i e n t s of which w e r e d e t e r m i n e d by a v a r i a t i o n a l p r o c e d u r e . R e s u l t s
w e r e obtained f o r the l e n g t h , v e l o c i t y , and a c c e l e r a t i o n dipole f o r m u l a t i o n s
of the o s c i l l a t o r s t r e n g t h . The s u m r u l e s f o r S 0 , S . j , S_ 2 , S_3 of Eq.(1.33)
w e r e used to t e s t the a c c u r a c y of the r e s u l t s . Good t h e o r e t i c a l c o n s i s t e n c y
and good a g r e e m e n t with e x p e r i m e n t w a s a c h i e v e d .
IAEA-SMR-12/50 701
T h e w o r k of Doughty e t a l . u s e s v a r i a t i o n a l ground s t a t e wave f u n c t i o n s ,

of the H y l l e r a a s and S c h w a r t z t y p e s , with an i n c r e a s i n g n u m b e r of p a r a -
m e t e r s (up to 20 f o r the H y l l e r a a s t y p e , and up to 70 f o r the S c h w a r t z type).
The c l o s e - c o u p l i n g method w a s then used to d e t e r m i n e the f i n a l - s t a t e wave
f u n c t i o n . An i n c r e a s i n g n u m b e r of i n t e r m e d i a t e s t a t e s w e r e included in the
c a l c u l a t i o n , the l a r g e s t b e i n g I s - 2s - 2p - 3s - 3p - 3d. Again, l e n g t h , v e l o c i t y ,
and a c c e l e r a t i o n dipole f o r m u l a t i o n s w e r e c o m p a r e d and the v e l o c i t y f o r m u l a -
tion w a s found s u p e r i o r . The a g r e e m e n t of the v e l o c i t y c u r v e s with e x p e r i m e n t i s
s t e a d i l y i m p r o v e d a s the e x p a n s i o n i s extended to the I s - 2s - 2p - 3s - 3p - 3d
a p p r o x i m a t i o n . It a l s o i m p r o v e s c o n s i d e r a b l y when including h i g h e r n u m b e r
of t e r m s in the ground s t a t e wave f u n c t i o n . The c a l c u l a t e d o s c i l l a t o r s t r e n g t h
a g r e e s with s u m r u l e s and e x p e r i m e n t to within about 5%. F i g u r e 4 p r e s e n t s
the b e s t t h e o r e t i c a l v a l u e s .
M o r e r e c e n t l y , Macek ( P r o c . P h y s . Soc. _92 (1967) 365) h a s u s e d a
I s - 2s - 2p c l o s e - c o u p l i n g wave f u n c t i o n to d e t e r m i n e the p h o t o - i o n i z a t i o n
c r o s s - s e c t i o n of H" in the neighbourhood of the t h r e s h o l d f o r l e a v i n g the
f i n a l h y d r o g e n a t o m in the n = 2 excited s t a t e . A s h a p e r e s o n a n c e was found
j u s t above the t h r e s h o l d (see F i g . 5 ) . H y m a n , J a c o b s and B u r k e (J. P h y s . В 5
(1972) 2282) have extended t h i s w o r k to c o n s i d e r t h e r e l a t i v e c o n t r i b u t i o n
to a b s o r p t i o n of the n = 2 s u b s t a t e s and have studied the a n g u l a r d i s t r i b u t i o n s
of the e j e c t e d p h o t o e l e c t r o n s .
B y c o m p a r i n g F i g s 3 and 4, one f i n d s a d r a s t i c d i f f e r e n c e in the
b e h a v i o u r of t h e c r o s s - s e c t i o n s at low e n e r g i e s , n e a r t h r e s h o l d . W h e r e a s
f o r He the c r o s s - s e c t i o n h a s a n o n v a n i s h i n g l i m i t at t h r e s h o l d , f o r H" the
c r o s s - s e c t i o n g o e s to z e r o . T h i s i s due to the f a c t t h a t in the c a s e of He
the f i n a l e l e c t r o n i s a s y m p t o t i c a l l y u n d e r the i n f l u e n c e of a C o u l o m b f i e l d ,
while in the c a s e of H~ it m o v e s in the field of the n e u t r a l H a t o m . ( F o r
d e t a i l s s e e R e f . [ 3 ] , Section 74 a ) .
REFERENCES
[ 1 ] AKHIEZER, A . J . , BERESTETSKY, V. B., Quantum Electrodynamics, Interscience (1965).

[ 2 ] BRANSCOMB, L. M . , "The photoionization of o n e - a n d two-electron atoms", Physics of the One-
and Two-Electron Atoms, North-Holland (1969), BOPP and KLEINPOPPEN, Eds.
[3] BETHE, H . , SALPETER, E . , Quantum Mechanics of One- and Two-Electron Atoms, Springer (1957).
[ 4 ] FANO, U . , COOPER, J . , Spectral distribution of atomic oscillator strengths, Rev. Mod. Phys. 40
(1968) 4410.
[ 5 ] MESSIAH, A . , Quantum mechanics, North-Holland (1961), Vols I, II.
[ 6 ] MARR, G . , Photoionization Processes in Gases, Academic Press (1967).
[7] SOMMERFELD, A . , Atombau und Spektrallinien, Viewe g (1960), Vol.11.
[ 8] STEWART, A. L., The quantal calculation of photoionization cross-sections, Adv. At. Molec. Phys. 3
(1967) 1.
[ 9 ] SMITH, K . , The Calculation of Atomic Collision Processes, Wiley (1971).
[10] BURKE, P . , "Low-energy electron-atom scattering", in Lectures in Theoretical Physics, Vol.XI С
(1968 Boulder Summer School), and "Analysis of electron-atom scattering and photoionization processes",
this volume.
ADDITIONAL BIBLIOGRAPHY
[11] CAIRNS, R.B., HARRISON, H . , SCHOEN, R. I . , Photoionization with molecular beams, Adv. At. Mol.
Phys. 8 (1972) 131.
[12] PRATT, R . H . , RON, A . , TSENG, H . K . , Atomic photoeffect above 10 keV, Rev. Mod. Phys. _45 (1973) 273.
[13] WEISSLER, G. L., "Photoionization in gases and photoelectric emission from solids", Encyclopedia of Physics
(FLÜGGE, S . , Ed.), 21 Springer, Berlin ( 1956) 304.
F A C U L T Y AND P A R T I C I P A N T S
DIRECTORS
Laboratoire de physique E . N . S . ,
A. Kastler 24 rue Lhomond,
Paris 5e, France
Institute of Physics, Sweden

B. Edlën University of Lund,
Lund, Sweden
Department of Atomic Physics, Hungary

I. Kovács Polytechnical University,
Budafoki ut. 8,
Budapest 1111, XI, Hungary
B.L. Moiseiwitsch Department of Applied Mathematics United Kingdom

and Theoretical Physics,
The Queen's University,
Belfast BT7 INN, Northern Ireland
L E C T U R E R S AND SEMINAR L E C T U R E R S
G. Amať , ! Université de Paris VI, Tour 13,

11 quai Saint-Bernard,
Paris 5e, France
G. Backenstoss'1' CERN-NP, Switzerland

1211 Genève 23, Switzerland
}. Bauche Laboratoire Aimé Cotton, Bât. 505,

Université Paris-Sud,
91-Orsay, France
J. Bradley Department of Pure and Applied Physics, United Kingdom

(see page 2)
J. Brossel:'' Laboratoire de Physique E. N. S . ,

24 rue Lhomond,
Paris 5e, France
P. G. Burke Department of Applied Mathematics and United Kingdom

Theoretical Physics,
Not published in these Proceedings.
703
704 FACULTY AND PARTICIPANTS
C. Cohen-Tannoudji* Laboratoire de Physique E.N. S. , France

24 rue Lhomond,
Paris 5e, France
J. Danon^ Centro Brasileiro de Persquisas Fisicas, Brazil

Av. Wenceslau Bras 71 - ZC82,
Rio de Janeiro, GB-Brazil
B. Edlén Institute of Physics, Sweden

University of Lund,
Lund, Sweden
S. Feneuille Laboratoire Aimé Cotton, Bât. 505, France

91-Orsay, France
F. Ferrari'' 4 Istituto di Fisica, ' Italy

Facolta die Scienze,
Università degli Studi,
Bari, Italy
M. Gavrila Facultatea de Fizica, Romania

Str. Academiei 14,
Bucarest, Romania
A. Gozzini' ,: Istituto de Micro-Onde, Italy

Universitä di Pisa,
Piazza Torricelli n"2,
Pisa, Italy
H. Haken Institut für theoretische Physik, Federal Republic

Universität, of Germany
Azenbergstrasse 12,
7 Stuttgart 1, Fed. Rep. of Germany
G. Herzberg' ,: National Research Council of Canada, Canada

Division of Physics,
Ottawa K1A 0R6, Canada
W.R. Hindmarsh Department of Atomic Physics, United Kingdom

University of Newcastle upon Tyne,
Newcastle upon Tyne NE1 7RU, UK
P. Jacquinot v Laboratoire Aimé Cotton, Bât. 505, France

91-Orsay, France
A. Kastler Laboratoire de physique E. N. S., France

24 rue Lhomond,
Paris 5e, France
L. Klynning Institute of Physics, Sweden

University of Stockholm,
Vanadisvägen 9,
Stockholm, Sweden
I. Kovács Department of Atomic Physics, Hungary

Budafoki ut. 8,
Budapest 1111, XI, Hungary
705 F A C U L T Y A N D P A R T I C I P A N T S
Mme H. Lefebvre-Brion Laboratoire de photophysique moléculaire,

Bât. 213,
91-Orsay, France
R. McCarroll Laboratoire d'astrophysique,

Université de Bordeaux-I,
40 rue Lamartine,
33-Talence, France
B. L. Moiseiwitsch Department of Applied Mathematics United Kingdom

I . C . Percival Physics Department, United Kingdom

The University of Stirling,
Scotland
F.H. Read Physics Department, United Kingdom

The University of Manchester,
Manchester, UK
M.J. Seaton Department of Physics, United Kingdom

University College,
Gower Street,
London WCIE 6BT, UK
O. Sinanoglu Department of Chemistry, United States

Yale University, of America
225 Prospect Street,
New Haven, Con. 06520, USA
PARTICIPANTS
N. Ahmad Electronics Division, Pakistan

PINSTECH,
P.O. Nilore,
Rawalpindi, Pakistan
J. Antó Roca Departamento de Optica, Spain

Facultad de Ciencias (Fisicas),
Univ. de Barcelona (Pedralbes),
Barcelona, Spain
E. Arimondo Istituto di Fisica, Italy

Piazza Torricelli 2,
56100 Pisa, Italy
G. L. Astner Research Institute for Physics, Sweden

Stockholm 50, Sweden
M . C . Attard They Royal University, Malta

Malta
A . I . Babalola Physics Department, Nigeria

University of Iba dan,
Ibadan, Nigeria
A. Baczyfiski Nicolas Copernicus University, Poland

Torurt, Poland
A . G . Bambini Laboratorio di Elettronica Quantistica Italy

del C . N . R.,
Via Panciatichi 56,
Firenze, Italy
S. Beg Institute of Physics, Pakistan

University of Islamabad,
P.O. Box 1090,
Islamabad, Pakistan
M. Berrondo Instituto de Ffsica, Mexico

Apartado Postal 20-364,
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M.S. - Z . Chaghtai Physics Department, India

Muslim University,
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Naresh Chandra Department of Applied Mathematics India

Queen's University,
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L. Colombo Institute "Ruder Boskovič", Yugoslavia

P.O. Box 1016,
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R. Corbalan Yuste Departamento de Ffsica Fundamental Spain

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P.O. Box 522, '
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Universidade Federal de Pernambuco,
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Torufi, Poland
M. A. de Moura Instituto de Fisica, Brazil

Universidade Federal de Pernambuco,
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J. Désesquelles Laboratoire de physique de l'atmosphère, France

Université de Lyon,
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G. Ferraro Laboratorio di Ricerche Sulla, Italy

Combustione del С. N. R.,
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W . C . Fon Department of Mathematics, Malaysia

University of Malaya,
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R. I. M. G. Forneris Departamento de Ffsica, Brazil

Instituto Tecnologico de Aeronautica,
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Tradgârdsgatan 18,
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P.O. Froman Institute of Theoretical Physics, Sweden

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M. Binderly Gaspar Centro Brasileiro de Pesquisas Ffsicas, Brazil

Av. Wenceslau Braz. 71 - fundos,
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A. Halpern Physics Dept. United States

Brooklyn College of the City University of America
of New York,
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(at ICTP up to end of 1973)
Т.Е. Horton, Jr. School of Engineering, United States

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S. Imam-Rahaju Department of Chemistry, Indonesia

Bandung Institute of Technology,
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and Technology,
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C . A . Massone Departamento de Ffsica, Argentina

Universidad Nacional de La Plata,
115 y 49, CC 67,
La Plata, Argentina
H. Mohan Department of Physics, India

University of Allahabad,
Allahabad 2, India
Mrs M. Mongy National Institute of Standards, Arab Republic

Dokki-Cairo, Arab Rep. of Egypt of Egypt
A. Monjazeb Physics Department, Iran

Allahabad University,
Allahabad 2, India
S. Mukamel Soreq Nuclear Research Centre, Israel

Yavne, Israel
S. C. Mukherjee Indian Association for the India

Cultivation of Science,
Jadavpur,
Calcutta 32, India
M. A. Naderi Faculty of Education, Afghanistan

Kabul University,
Kabul, Afghanistan
R. Nath Department of Physics and Astrophysics, India

University of Delhi,
Delhi 7, India
E.C. Njau Physics Department, Tanzania

University of Dar es Salaam,
P.O. Box 35063,
Dar es Salaam, Tanzania
A. Ouedraogo Centre d'études supérieures, Upper Volta

Ouagadougou В. P. 21,
Ouagadougou, Upper Volta
P. Pacher Department of Atomic Physics, Hungary

Budafoki u. 8,
Budapest XI, Hungary
H. Parsche Physics Department, Federal Republic

Technical University München, of Germany
Garching bei München,
Fed. Rep. of Germany
R. Paternoster Nuclear Engineering Sciences Department, United States

University of Florida, of America
202 Nuclear Sciences Center,
Gainesville, Fla. 32601, USA
Z . PavloviC Institute "Ruder Boskovič", Yugoslavia

Bijenicka 54,
41001 Zagreb, Yugoslavia
R. D.N. Piacentini Departamento de Ffsica, Argentina

Facultad de Ciencias Exactas e
Ingenierfa,
Universidad de Rosario,
Pellegrini 250,
Rosario, Argentina
M. Rafi Department of Physics, Pakistan

University of Karachi,
Karachi 32, Pakistan
W. Rasmussen Johns Hopkins University, United States

3400 North Charles St., of America
Baltimore, Md. 21218
V. Roberto Istituto di Fisica, Italy

Via Valerio,
Trieste, Italy
Miss A. Roche Laboratoire de photophysique moléculaire, France

Bâtiment 213,
91405 Orsay, France
K. M. Rzazewski Institute of Theoretical Physics, Poland

University of Warsaw,
ul. Hoza 69,
Warsaw, Poland
H. Saitovitch Centro Brasileiro de Pesquisas Ffsicas, Brazil

Av. Wenceslau Braz 71,
Rio de Janeiro, Guanabara, Brazil
K. Sathianandan Physics Department, India

Poona University,
Poona 7, India
710 F A C U L T Y AND P A R T I C I P A N T S
A. E. - T. Sharaf-el-Din Department of Physics, Sudan

Faculty of Science,
University of Khartoum,
Khartoum, Sudan
C.B. Shrestha Physics Department, Nepal

Tri-Chandra College,
Kathmandu, Nepal
O . N . Singh Institute of Technology, India

Banaras Hindu University,
Varanasi 5, India
P. Siicar Department of Physics, India

University of Kalyani,
Kalyani, West Bengal, India
Munit Sunnâ Directorate of Education, Jordan

Suit, Jordan
Suwatdi FIPIA - Universitas Indonesia, Indonesia

Salemba 4,
Jakarta, Indonesia
M. A. Thomas Department of Physics, United Kingdom

University College,
Gower Street,
London WC 1, England
A . N . Ttipathi Department of Physics, India

University of Roorkee,
Roorkee, India
Miss C. Tronçon Istituto di Fisica, Italy

Via Valerio,
Trieste, Italy
Sz. Vass Central Research Institute for Physics, Hungary

P.O. Box 49,
Budapest 114, Hungary
R. J. Vetter Laboratoire Aimé Cotton, France

C . N . R.S. II,
91-Orsay, France
J. Woodworth Physics Department, United States

Johns Hopkins University, of America
3400 North Charles S t . ,
Baltimore, Md. 21218, USA
W.B. Zakowicz Institute of Nuclear Research, Poland

ul Hoza 69,
Warsaw, Poland
CONVERSION TABLE:
FACTORS FOR CONVERTING UNITS TO SI SYSTEM EQUIVALENTS*
SI base units are the metre (m), kilogram (kg), second (s), ampere ( A ) , kelvin ( К ) , candela (cd) and mole (mol).
(For further information, see International Standards ISO 1000 ( 1 9 7 3 ) , and ISO 3 1 / 0 (19741 and its
several parts]
Multiply by to obtain
Mass
pound mass (avoirdupois) 1 Ibm = 4 . 5 3 6 X 10" 1 kg

ounce mass (avoirdupois) 1 ozm = 2 . 8 3 5 X 10 1 9
ton (long) (= 2 2 4 0 Ibm) 1 ton = 1.016 X 10 3 kg
ton (short) (= 2 0 0 0 Ibm) 1 short ton = 9.072 X 102 kg
tonne (= metric ton) 1 t = 1.00 X 10 3 kg
Length
statute mile 1 mile = 1.609 X 10° km

yard 1 yd = 9.144 X 10"' m
foot 1 ft = 3.048 X 10"1 m
inch 1 in = 2.54 X 10" 2 m
mil (= 10" 3 in) 1 mil = 2.54 X 10~ 2 mm
Area
hectare 1 ha = 1.00 X 10" m2

(statute mile) 2 1 mile 2 = 2 . 5 9 0 X 10° km2
acre 1 acre = 4 . 0 4 7 X 10 3 m2
yard 2 1 yd2 = 8 . 3 6 1 X 10" 1 m2
foot2 1 ft2 = 9 . 2 9 0 X 10~ 2 m2
inch 2 1 in 2 = 6 . 4 5 2 X 10 2 mm2
Volume
yard 3 1 yd3 = 7.646 X 10"' m3

foot3 1 ft3 = 2 . 8 3 2 X 10" 2 m3
inch 3 1 in 3 = 1.639 X 10" mm3
gallon (Brit, or Imp.) 1 gal (Brit) = 4.546 X 10~ 3 m3
gallon (US liquid) 1 gal (US) = 3.785 X 10" 3 m3
litre 1 1 = 1.00 X 10~ 3 m3
Force
dyne 1 dyn = 1.00 X 10~ s N

kilogram force 1 kgf = 9 . 8 0 7 X 10° N
poundal 1 pdl = 1.383 X 10" 1 N
pound force (avoirdupois) 1 Ibf = 4 . 4 4 8 X 10° N
ounce force (avoirdupois) 1 ozf = 2 . 7 8 0 X 10" 1 N
Power
British thermal unit/second 1 Btu/s = 1 . 0 5 4 X 10 3 W

calorie/second 1 cal/s = 4 . 1 8 4 X 10° W
foot-pound force/second 1 ftlbf/s = 1.356 X 10° W
horsepower (electric) 1 hp 7.46 X 10 2 W
horsepower (metric) (= ps) 1 ps = 7.355 X 10 2 W
horsepower ( 5 5 0 f t l b f / s ) 1 hp = 7.457 X 10 2 W
* Factors are given exactly or to a maximum of 4 significant figures

Multiply by to obtain
Density
pound mass/inch 3 1 lbm/in3 = 2 . 7 6 8 X 10 4 kg/m3

pound mass/foot 3 1 lbm/ft3 = 1 . 6 0 2 X 10 1 kg/m3
Energy
British thermal unit 1 В tu = 1.054 X 10 3

calorie 1 cal = 4 . 1 8 4 X 10°
electron-volt 1 eV 1.602 X 10'19
erg 1 erg = 1.00 X 10'7
foot-pound force 1 ft-lbf = 1.356 X 10°
kilowatt-hour 1 kWh = 3.60 X 10®
Pressure
newtons/metre 2 1 N/m2 = 1.00 Pa

atmosphere a 1 atm = 1.013 X 10 s Pa
bar 5
1 bar = 1.00 X 10 Pa
centimetres of mercury (0°C) 1 cmHg = 1.333 X 10 3 Pa
dyne/centimetre 2 1 dyn/cm 2
= 1.00 X 10" 1 Pa
feet of water (4°C) 1 ftH20 = 2.989 X 10 3 Pa
inches of mercury (0°C) 1 inHg = 3.386 X 10 3 Pa
inches of water (4°C) I 1 inH20 = 2.491 X 102 Pa
kilogram force/centimetre 2 1 kgf/cm2 = 9.807 X 10 4 Pa
pound force/foot 2 1 lbf/ft2 = 4.788 X 10 1 Pa
2 0
pound force/inch (= psí) 1 lbf/in2 = 6.895 X 10 3 Pa
torr (0°C) (= mmHg) 1 torr = 1.333 X 10 2 Pa
Velocity, acceleration
inch/second 1 in/s = 2.54 X 10 1 mm/s

foot/second (= fpsl 1 ft/s = 3 . 0 4 8 X 10"' m/s
foot/minute 1 ft/min = . 5 . 0 8 X 10" 3 m/s
[4.470 X 10"' m/s
mile/hour |= mph) 1 mile/h
[1.609 X 10° km/h
knot 1 knot = 1.852 X 10° km/h
free fall, standard (= g) = 9.807 X 10° m/s 2
foot/second 2 1 ft/s 2 = 3.048 X 10"' m/s 2
Temperature, thermal conductivity, energy/area• time
Fahrenheit, d e g r e e s - 3 2 °F-32\ 5 f°C

Rankine °R J 9 \ К
1 Btu i n / f t 2 s - ° F = 5 . 1 8 9 X 10 2 W/m-K
1 Btu/ft-s- ° F = 6.226 X 10' W/m-K
1 cal/cm-s-°C = 4 . 1 8 4 X 10 2 W/m K
1 Btu/ft2s = 1.135 X 10 4 W/m2
1 c a l / c m 2 min = 6.973 X 102 W/m2
Miscellaneous
foot 3 /second 1 ft3/s = 2.832 X 10-J m3/s

foot3/minute 1 ft3/min :
= 4.719 X 10" m3/s
rad rad = 1.00 X 10"' J/kg
roentgen R = 2.580 X 10" 4 C/kg
curie Ci = 3.70 X 10 1 0 disintegration/s
atm abs: atmospheres absolute ^ l b f / i n 2 (g) (= psig): gauge pressure; 05
atm (g): atmospheres gauge. I b f / i n 2 abs (= psia): absolute pressure. S

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Atoms, Molecules

Owing to postal difficulties outside the publisher's control, the

RADIOFREQUENCY SPECTROSCOPY, by A. Kastler (pp. 175-211)

Page 202, Fig. 24. Delete parts (b) and (c).

Page 622, line above Eq.(1.15). For ( 1.15) read (1.14). 2m

ATOMS, MOLECULES AND LASERS

INTERNATIONAL ATOMIC E N E R G Y AGENCY

ATOMS, M O L E C U L E S AND LASERS

Printed by the IAEA in Austria

The papers and discussions incorporated in the proceedings published

THEORY O F ATOMIC STRUCTURE

THEORY OF ATOMIC STRUCTURE AND TRANSITION PROBABILITIES.

To avoid r e p e a t i n g m a n y t i m e s the n o t a t i o n s to be u s e d and to give

If we u s e t h e a p p r o x i m a t i o n s defined in s u b s e c t i o n 1.1, the n o n - r e l a t i v i s t i c

S, M s , L , M L a r e no l o n g e r good q u a n t u m n u m b e r s . Now, if we d e f i n e the

H o w e v e r , in m a n y c a s e s t h i s a p p r o x i m a t i o n i s not valid a s , e . g . f o r noble

Ho = ^ (Pj) 2 - e U ( r j )j- (principal Hamiltonian)

a r e l a b e l l e d by the two q u a n t u m n u m b e r s n and Í ( i < n , i n t e g e r s ) while

I n s m s < i B ( ) = -i R n f ( r ) I s mj > \ i т { >

|üm { ]> = Y í r r ] í (6,9), ( s p h e r i c a l h a r m o n i c ) , | s m s ) > (spin f u n c t i o n )

In any c a s e , ( n - i - 1 ) is t h e n u m b e r of n o d e s of R n i ( r ) excluding o r i g i n and

E n e r g y l e v e l s of Ho. The d i s c r e t e e i g e n v a l u e s of H 0 can be w r i t t e n

N(nje) S (4Í +2)

Giving the n u m b e r s N(ni) i s e q u i v a l e n t to d e f i n i n g an e l e c t r o n c o n f i g u r a t i o n

The e n e r g y m a t r i x . In a f i r s t a p p r o x i m a t i o n , the e n e r g y l e v e l s belonging

1.4.2. Hartree-Fock approximation

The key idea of t h i s type of a p p r o x i m a t i o n is b a s e d on the f a c t that the

The H a r t r e e - P o c k f u n c t i o n is of the s a m e type and t h e r e f o r e only the r a d i a l

If we change r into p = r Z , p b e c o m e s Ťr = ( l / Z ) p and t h e r e f o r e the n o n -

To give the n u m b e r N(n) i s e q u i v a l e n t to t h e d e f i n i t i o n of a c o m p l e x

1.5. C o n c l u s i o n and c o n t e n t s of the p a p e r

The m a i n p r o b l e m in the t h e o r y of a t o m i c s t r u c t u r e is to c a l c u l a t e the

A g r o u p i s a s e t (finite o r infinite) of e l e m e n t s R j ... R g ... which

If it i s p o s s i b l e to find a m o n g the e l e m e n t s of a g r o u p G a s u b s e t which

2.1.3. Direct product

If t h e e l e m e n t s of two g r o u p s G f R j R g ...) and G ' i R ' j R ^ ...) c o m m u t e

Two g r o u p s G and H a r e said to be i s o m o r p h i c if a unique c o r r e s p o n d e n c e

If the c o r r e s p o n d e n c e i s not unique, and if one and only one e l e m e n t

The e l e m e n t R T = R p R 0 R" p 1 i s said t o ' b e c o n j u g a t e to R 0 . A s e t of

Tr(R0RT) = ^ r ; j (d)r j i (T)= T r ( R p R 0 )

Such a t r a c e i s c a l l e d a " c h a r a c t e r " and it h a s the s a m e v a l u e a s all the

w h e r e m and n do not depend on ст.

(Гк o c c u r s CR t i m e s in the d e c o m p o s i t i o n of T w ) and can be e x p r e s s e d

(a) If R 0 and Q 0 f o r m two i n e q u i v a l e n t i r r e d u c i b l e m a t r i x r e p r e s e n t a -

f o r a l l ст, t h e n A i s a c o n s t a n t m u l t i p l i e d by the unit m a t r i x . It f o l l o w s f r o m

X rij(CT)qVCT) = 0 for a11

It f o l l o w s f r o m (b) t h a t , ' i f a l l the m a t r i c e s of an i r r e d u c i b l e r e p r e s e n t a t i o n

w h e r e g i s the n u m b e r of e l e m e n t s of the c o n s i d e r e d g r o u p and n r i s the

Cj " ~ ^ x(Cir{ ) x*(C;rj )

L e t u s s u p p o s e that the n f u n c t i o n s фг , фj, ... фп f o r m a b a s i s of a r e p r e

The b a s i s f u n c t i o n s of Г к can be w r i t t e n a s l i n e a r c o m b i n a t i o n s of the

The c o e f f i c i e n t s ( ; |) a r e called C l e b s c h - G o r d a n c o e f f i c i e n t s . If the

T h i s t h e o r e m i s f u n d a m e n t a l in o r d e r to apply group t h e o r y to the

and t h a t the f o l l o w i n g conditions a r e s a t i s f i e d :

Any f i n i t e r o t a t i o n about R ( a , f ) c a n be w r i t t e n in t e r m s of a and I In

L e t u s now c o n s i d e r an i n f i n i t e s i m a l r o t a t i o n by do about t h i s a x i s can

R ( d a , £ ) = R(do s i n 0 cos cp, x) R(da sin 0 s i n cp, y) R ( c o s 0 d « , z )

So, t h e i n f i n i t e s i m a l o p e r a t o r s add like v e c t o r s and any r o t a t i o n can be

Fig. 2. Finite rotation R(a, £,).

ily ~ Ixlz ~ I^^-X