5.

61 Fall 2004 Lecture #17-19 page 1

THE RIGID ROTOR

Diatomic molecule

r1 + r2
r0
m1
r1 mrmr=
(center of mass)
COM r2 m2

K.E. K=
1
2
1 1
(
m1r12 2 + m2 r22 2 = m1r12 + m2 r22  2
2 2
)
I  moment of inertia
1 2

K= I
2

m1 m2
I = m1r12 + m2 r22 = µ r02 µ= (reduced mass)
m1 + m2

1 2 2 1 2
K= µ r  = µ v0
2 0 2
z

Problem reduced to
a one-body problem
µ
with mass µ. r0


y


x
5.61 Fall 2004 Lecture #17-19 page 2

Angular momentum L=r
p

L = L = r1 p1 + r2 p2 = m1r1v1 + m2 r2 v2 = m1r12 + m2 r22 = I 

1 2 L2

K = I =
2 2I

Connection between angular momentum and kinetic energy for rotation

Analogous to linear momentum and kinetic energy for translation

Now need to describe this quantum mechanically.

2 2
(
H = K + V x, y, z =

ˆ )
 + V x, y, z
2 µ xyz
( )
2 2 2
 2xyz = + +
x 2 y 2 z 2

Change to spherical polar coordinates

Cartesian  spherical polar

( x, y, z )  ( r, ,
)
x = r sin  cos

y = r sin  sin

z = r cos 

1  2  1   1 2
 2
= 2 r + 2 sin  + 2 2
r r  r r sin   
r

 r sin  
2

so in spherical polar coordinates ( ) ( )

Hˆ r, ,
 r, ,
= E r, ,
( ) is
5.61 Fall 2004 Lecture #17-19 page 3

⎪⎧  ⎡ 1 ∂ ⎛ 2 ∂ ⎞ ∂ ⎛ ∂⎞ ∂2 ⎤ ⎫
2

⎨− ⎢ 2 ⎜r ⎟+ 2
1 1
⎜ sinθ ∂θ ⎟⎠ + r 2 sin2 θ ∂φ 2 ⎥ + V r,θ , φ ( )⎪⎬ψ ( r,θ ,φ )
⎪⎩ 2 µ ⎣ r ∂r ⎝ ∂r ⎠ r sin θ ∂θ ⎝ ⎦ ⎪⎭
(
= Eψ r,θ , φ )
In our rigid rotor example

( )
V r,θ , φ = 0 (r = r ) 0
i.e. r is held constant at r0.
V ( r,θ , φ ) = ∞ ( r ≠ r ) 0

(
ψ r,θ , φ ) → (
ψ r0 ,θ ,φ )
∂
∂r
( )
ψ r0 ,θ , φ = 0

Rewrite Schrodinger eq. without variable r:

2 ⎡ 1 ∂ ⎛ ∂⎞ 1 ∂2 ⎤
− ⎢ ( )
⎜ sin θ ∂θ ⎟⎠ + sin 2 θ ∂φ 2 ⎥ ψ r0 ,θ ,φ = Eψ r0 ,θ , φ ( )
2 µ r02 ⎣ sin θ ∂θ ⎝ ⎦
I

Set ( ) ( )
ψ r0 ,θ , φ = BY θ , φ
Need to solve

2 ⎡ 1 ∂ ⎛ ∂⎞ 1 ∂2 ⎤
− ⎢ ( )
⎜ sinθ ∂θ ⎟⎠ + sin 2 θ ∂φ 2 ⎥ Y θ , φ = EY θ , φ ( )
2I ⎣ sin θ ∂θ ⎝ ⎦
5.61 Fall 2004 Lecture #17-19 page 4

SOLUTIONS TO THE RIGID ROTOR

Solving for the rigid rotor problem, we are now left with solving the diff. eq.

2 ⎡ 1 ∂ ⎛ ∂⎞ 1 ∂2 ⎤
−
2I
⎢
sin θ ∂θ
( ) ( )
⎜⎝ sinθ ∂θ ⎟⎠ + sin 2 θ ∂φ 2 ⎥ Y θ , φ = EY θ , φ
⎣ ⎦

This is ( ) ( )
ĤY θ , φ = EY θ , φ

with Ĥ = K̂ since the potential Vˆ = 0

Rearranging the diff. eq.

⎡ ∂ ⎛ ∂ ⎞ 2IE 2 ⎤ ∂2
⎢sinθ
∂θ
( )
⎜⎝ sinθ ∂θ ⎟⎠ +  2 sin θ ⎥ Y θ ,φ = − ∂φ 2 Y θ , φ( )
⎣ ⎦

only θ only φ

We’ve separated the variables, just as in the 3D particle in a box problem.

∴ Try ( ) () ()
Y θ ,φ = Θ θ Φ φ as a solution

2IE
Define β≡
2
( note β ∝ E )
⎡ ∂ ⎛ ∂⎞ ⎤ ∂2
⎢sinθ
∂θ
() ()
⎜⎝ sinθ ∂θ ⎟⎠ + β sin θ ⎥ Θ θ Φ φ = − ∂φ 2 Θ θ Φ φ
2
() ()
⎣ ⎦

Dividing by Θ θ Φ φ ( ) ( ) and simplifying

sin θ ∂ ⎛ ∂⎞ 1 ∂2
()
sin θ ⎟ Θ θ + β sin θ = −
2
Φ φ ()
()
Θ θ ∂θ ⎜⎝ ∂θ ⎠ Φ φ ∂φ 2 ()
only θ only φ
5.61 Fall 2004 Lecture #17-19 page 5

Since  and  are independent variables, each side of the equation must be
equal to a constant  m2.

2
1
  =
m2 () I
()
   2

sin   
and sin 
 +  sin 2  = m2 () II
()

   

First solve for
 using() I

( ) =
m  
2  
 2 () 2

()
Solutions are   = Am e
im
and A
m e
im

Boundary conditions quantization

(

 + 2 =
 ) ()
(
im  + 2 ) (

im  + 2 )
Am e = Am eim and A
m e = A
m e
im

( )
im 2 ( )

im 2

e = 1 and e =1

This is only true if m = 0, ± 1, ± 2, ± 3,....

m is the “magnetic” quantum number

()

 = Am eim m = 0, ± 1, ± 2, ± 3,....

() ()
2
Normalization: 
0

   d = 1
5.61 Fall 2004 Lecture #17-19 page 6

 =() 1
eim m = 0, ± 1, ± 2, ± 3,...
2
()
Now let’s look at
 . Need to solve II

sin  
sin  ()

 +  sin2  = m2
() 

   

Change variables: x = cos    =P x() () dx

sin 
= d

Since 0     
1  x  +1

Also sin 2  = 1
cos 2  = 1
x 2

After some rearrangement we obtain the Legendre equation ……

 m2 
(1
x )
2 d2
dx 2
() d
P x
2x P x +  

dx

()
2 
P x =0 ()
 1 x 

The continuity of
 () constraint leads to a quantization for .

(

= l l +1 ) where l = 0, 1, 2,...
and m = 0, ± 1, ± 2,..., ±l

This directly leads to quantization for the energy!

2 IE
2

= 2  E=


2I

2
E=
2I
(
l l +1 ) l = 0, 1, 2,... (for rigid rotor, use J instead of l)

2
EJ =
2I
J J +1 ( ) J = 0, 1, 2,...
5.61 Fall 2004 Lecture #17-19 page 7

m
Solutions of Legendre eq. are associated Legendre polynomials Pl

Pl
m
( x ) = P (cos
)
l
m

( ) P ( cos ) = ( 3cos 
1)
1
P00 cos = 1 2
0 2

2
P ( cos ) = cos 
1
0
P (cos  ) = 3cos  sin 
2
1

P ( cos  ) = sin 
1
1
P ( cos  ) = 3sin 
2
2 2

etc.

()
So   = Alm Pl
m
(cos )
 2l + 1
Alm = 
( l
m )! 2

 2 ( l + m )!
where Alm is the normalization constant
2

( )


Alm2   Pl cos   sin  d = 1
m
0  

So now putting it all together:

( ) ( )
 lm r0 , , = Yl m  ,  = l 
m 
m
() ()
1

Yl m
( )
 2l + 1
 , = 
( l
m )! 2

Pl
m
(cos ) e im

 4 ( l + m )!
These functions are called spherical harmonics.

They are the eigenfunctions of ĤY = EY for the rigid rotor.

5.61 Fall 2004 Lecture #17-19 page 8

1
1 3 2
Y00 = Y11 =  sin  ei
( 4 )  8
12

1 1
3 2 3 2
Y10 =  cos  Y1
1 = sin e
i
 4  8
etc.
SPHERICAL HARMONICS

( ) m
Yl m  ,  = l 
m  () ()
1

Yl m
( )
 2l + 1
 , = 
( l
m )! 2

Pl
m
(cos ) e im

 4 ( l + m )!
l = 0, 1, 2,... m = 0, ± 1, ± 2, ± 3,... ± l

Yl m ’s are the eigenfunctions to Ĥ
= E
for the rigid rotor problem.

1
5 
1
(3cos 
1)
2
Y00 = Y20 =  2

( 4 )  16
12

1 1
3 2 15  2
Y10 =  cos  Y2±1 = sin  cos  e±i
 4  8
1 1
3 2 15  2 2 ±2i
Y11 =  sin  ei Y2±2 = sin  e
 8  32
1
3 2
Y1
1 = sin  e
i
 8

Yl m ’s are orthonormal:  Y ( , )Y ( , ) sin d d =   mm

m
m
l l ll 

1 if l = l 1 if m = m normalization
Krönecker delta
ll  = 
mm = 
0 if l  l  0 if m  m orthogonality
5.61 Fall 2004 Lecture #17-19 page 9

Energies: ˆ m = E Ym)
(eigenvalues of HYl lm l
Switch l
J conventional for molecular rotational quantum #

Recall
2 IE
(

= 2 = l l +1  J J +1


) (
J = 0, 1, 2,... )

2

EJ =
2I
J J +1 ( )

J=2

2
J=1 E1 =
I
(
Y10 , Y1±1 3x degenerate )
J=0 E0 = 0 (
Y00 nondegenerate )
Degeneracy of each state (
g J = 2J + 1 )
from m = 0, ± 1, ± 2,..., ± J

Spacing between states as J

2
2
E J +1
E J = ( )(
 J +1 J + 2
J J +1  =
2I 
)
 I J +1 ( ) ( )
Transitions between rotational states can be observed through
spectroscopy, i.e. through absorption or emission of a photon

+ +
h Absorption
EJ EJ+1
- -

+ +
or Emission h
EJ EJ-1
- -
5.61 Fall 2004 Lecture #17-19 page 10

Molecules need a permanent dipole for rotational transitions.

Oscillating electric field grabs charges and torques the molecule.

2
dµ
( )

Strength of transition I JJ   
J    µ  J dx
dx 

electric field dipole moment

of radiation of rotor

Leads to selection rule for rotational transitions:
J = ±1

Recall angular momentum is quantized (in units of
).

Photon carries one quantum of angular momentum.
Conservation of angular momentum
J = ±1
Angular momentum of molecule changes by 1 quantum upon absorption or
emission of a photon.

2
E photon = h photon = Erot
J  J +1 J  J +1
= E J +1
E J =
I
J +1 ( )
photon =
J  J +1
h
4 2 I
(
J +1 )
Define the rotational constant B
h h
B (Hz) or B (cm-1)
8
2 I 8
cI
2

(

J  J +1 (Hz) = 2 B J + 1 ) (

J  J +1 (cm -1 ) = 2B J + 1 )
E

J=3 E3 = 12 Bhc

E2 3 = 6Bhc

J=2 E2 = 6Bhc

E12 = 4Bhc
J=1 E1 = 2 Bhc

E01 = 2 Bhc
5.61 Fall 2004 Lecture #17-19 page 11

This gives rise to a rigid rotor absorption spectrum with evenly spaced lines.

2B

01
12
23
34
45
56

Spacing between transitions is 2 B (Hz) or 2B (cm -1 )

( ) (
 J +1 J + 2
 J  J +1 = 2 B  J + 1 + 1
2B J + 1 = 2B )
Use this to get microscopic structure of diatomic molecules directly from
the absorption spectrum!

Get B directly from the separation between lines in the spectrum.

Use its value to determine the bond length r0 !

h m1 m2
2B = I = µ r02 µ=
4
2 cI m1 + m2

1 1
 h  2  h  2

r0 =  2 -1
 (B in cm ) or r0 =  2  (B in Hz)
 8
cB µ   8
B µ