Journal of Molecular Structure.

39
Elsevier Publishing Company, Amsterdam. Printed in the Netherlands

CRYSTAL FIELD ASPECTS OF VIBRATIONAL SPECTRA

IV. THE EFFECT OF &ORBITAL SPLITTING ON THE INFRARED
SPECTRA OF TRANSITION METAL(I1) COMPLEXES OF c&CHELATING
BIDENTATE LIGANDS

G. C. PERCY AND D. A. THORNTON

Department of Chemistry, University of Cape Town (South Africa)

(Received March 26th, 1971)

ABSTRACT

The infrared spectra of fifty-one complexes of c&chelating bidentate ligands

with metal(H) ions of the first transition series are discussed; Four bands below
600 cm-‘_ in the spectra of the complexes [M(bipy)s](ClO& and [M(phen)3]
(ClO.& (bipy = 2,2’-bipyridine, phen = l,lO-phenanthroline) exhibit a frequency
variation which para!Iels the variation of crystal field stabilization energy with d-
orbital configuration and therefore suggests their assignment to metal-nitrogen
stretching frequencies, v(M-N). The derangement of the normal Irving-Williams
stability order resulting from the occurrence of spin-paired Cr(I1) and Fe(I1) is
reflected by the order of v(M-N): Cr > Mn e Fe > Co < Ni > Cu > Zn.
v(M-N) and v(M-0) for the complexes [M(N-N)(AA),] (N-N = bipy, phen,
biquinolyl; AA = acetylacetonate) are assigned by comparison with the spectra
of CM(N-N), I (ClO& and K[M(AA),]. Both frequencies exhibit the metal ion
dependence predicted by crystal field theory.

INTRODUCTION

It is now well established ‘32 that the metal-ligand stretching frequencies,

v(M-L), of a series of complexes of first transition series metal ions vary with d-
orbital population in a way which parallels the variation of their crystal field
stabilization energie? (CFSE’S). Metal(H) complexes for which this relationship has
been shown to exist are exemplified largely by those containing monodentate ali-
phatic, aromatic and heterocyclic amine ligands. There are very few series of com-
plexes of this type in which all of the preparatively accessible members are iso-
structural. For instance, in the series [Man,Cl,], (an = aniline), the Mn(I1) and
Ni(II) derivatives have polymeric octahedral co-ordination, the Co(H) and Zn(I1)
compIexes are monomeric and tetrahedral and the Cu(II) compound is tetragonal’.
J: Mol. Structure, 10 (1971) 39-48
40 G. C. PER&, D. A. THORNTON

One way of achieving an isostructural series is by employing a bidentate ligand

which is incapable of spanning tram positions. Common examples are bipy and
phen., Here we report the IR spectra of the complexes [M(N-N),](CIO,),
(N-N = bipy, phen) representing two series of complexes for which each of the.
3d4-3d” metal(H) derivatives is isostructural. These complexes have two further
points of interest: the Fe(H) and Cr(I1) derivatives are spin-paired and the com-
pound CCu(phen)d(CO& is. prevented from being tetragonally distorted by the
inflexibility of the bidentate ligand3. The work has been extended to include the
compounds [M(N-N)(AA),] (AA = acetylacetonate ion; (N-N) = bipy or phen
or biquin). In these compounds two of the cis-bidentate nitrogen donors are
replaced by the cis-bidentate oxygen donor, acetylacetonate. Complexes studied
are represented by formulae (I-III).

1
O--l -
o--b~
’
,’
f, M :
&c_ _>d
[ A’ 1
(II) (1111

&igands used

N-N o-o

Q--Q 2.2’-bipyridinc lbipy)

H3c71-*3
0 6-
rcctylrcctonatr IAA)

pQ l.lO-phenanthmlinc lphcnl
F3CY-+rCH3
G 0-
trifl~crtylacctcmtc 1TFAj

H5cslfYcH3
0 0-

H5c61fYc6Hs
0 0-
dibcnzoylmcthanatc UIBMI

EXPERIMENTAL

The compounds [M(N-N),](CIO,), , many of which have been reported4 -6,

were prepared by the following general method. A hot aqueous solution of the
metal sulphate (Ig) ( or; ‘exceptionally, chromium(I1) acetate or iron (II) am-
monium sulphate for the Cr(I1) and Fe(I1) ccmplexes) was added to a hof aqueous
solution of the .ligand (3 molar proportions). Addition of an. excess. of .tiqueous
KC104 irecipitated the product-which .was collected; washed .(w.ater). and dried

J. MoL Structure, 10. (1971) 3943

CRYSTAL FIELD ASPECTS OF VIBRATIONAL SPECTRA. IV. 41

over silica gel at 20-25 “C and 0.1 mm Hg pressure. A 4:l bipy : CuSO, - SH,O
molar ratio is necessary to obtain [Cu(bipy),](ClO,),;
The newly reported complexes [M(biquin)(AA),] were-prepared by methods
analogous to those described7 for [M(bipy)(AA),] and [M(phen)(AA),].’ The
complexes K[M(TFA),], K[M(BA),] and K[M(DBM),], also newly described;
were prepared by procedures similar to those reported7 for K[M(AA),]. Composi-
tion and purity of all compounds were determined by microanalysis: Infrared
spectra were determined on Nujol mulls between caesium bromide plates (or,
below 300 cm- ‘, between polyethylene plates) on a Beckman IR-12 spectiophoto-
meter calibrated against carbon dioxide and water vapour. For maximum preci-
sion, frequencies were read from the wavenumber drum, not from the chart paper.
Reproducibility is within 1 cm-’ for niost bands.

RESULTS AND DISCUSSION

In octahedral co-ordination, the CFSE is a function of the magnitude of 1ODq

and the mode of occupation of the t,, and ea orbitals. These are not entirely in-
dependent variables since a ligand with sufficiently high ligand field strengtg will
enforce maximum occupation of the t,, orbitals. Alternative spin states are possible
only for d4-d7 ions. The majority of octahedral complexes of 3d4-3d7 ions are
spin-free except for Co(lIII) which is invariably spin-paired. In practice, a series
of complexes containing all the isovalent ions with 3d0-3d1’ configuration cannot
be synthesized but a hypothetically complete series in which the 3d4-3d7 ions are
spin-free yields calculated CFSE'S in the order

.d” < d’ < dZ < d3 > d4 > d= < d6 < d7 < dg > dg > d”.

The v(M-L) values of the majority of transition’metal(II) and -(III) complexes

thus far studiedIS exhibit this order except where Jahn-Teller distortion leads to
additional stabilization. In the relatively few series where the d4-d7 ions have spin-
paired configuration, the CFSE order becomes

do < d1 < d2 < d3 < d4 < d= < d6 < d7 < da > dg > dl’.

Only two series (with only four or five members in each) have been cited’ where
the v(M-L) values follow this order. These are the first transition series metal(III)
cyanide complexes, K, [M(CN),], and the- second transition series metal(II1)
acetylacetonates, [M(AA)3]. In the former, the strongly n-bonding cyanide lig&d
and in the latter, the increased spread of the 4d orbitals relative to the 3d, increase
1ODq sufficiently to enforce spin-paired configuration.
Because the gain in orbital energy in a strong field is identical for 3d5-and 3d6
ions while the gain in the exchange energy is greater for the 3d6 ion, spin pairing is
readily induced in the 3d’ ions F&(11) and Co(III). Thus, in the series [M(AA),]

J. Mol. Srmcrure,10 (1971)39-48

TABLE 1
CFSE, THERMODYNAMIC AND INFRARED DATA

Pbranreter Ca Cr Iv/t Fe CO Ni C/l 211

3d0 3d4 3d5 3d6 3d’ 3llS 3d” 3d’O
--
g iW” 14.1 8.5 10.0 9.3 8.9 12.0
-CFSE, [M(N-N)J]2 + series 0 I 6Dqb 0 24Dqb 6Dq l2Dq 6Dq 0
t,-k~~~, all other series 0 6Dq 0 4Dq 6Dq 1204 6Dq 0

3.27 5.98 0 4.85 3,lO

-CCPSE (kK) cf= 1,43)’ 32.3 0 34,3 8.0 l5,3 10.3 0
log /L* J 1.47 17,45 16.02 20454 17.08 13.63
-AH (kcal mole’ l)O 18.1 2800 19,7 26.7 21.6 J 5.9
-AH (kcal mole’ l)d 31.4 21,3 2802 23,8 Il.5
297 (-) 239 (Oj 295 (56) 265 (26) 295 (56) 280’ (41) 239 (0)
361 (-) 356 (0) 380 (23) 362 (4) 362 (4) 3550 (- 4) 360 (0)
v(M-N) and (v-vo) (cm- I)
410 (-) 409 (0) 419 (8) 413 (I) 415 (1) 410 (- 6) 418 (0)
426 (-) 417 (0) 477 (62) 434 (13) 440 (I 3) 434h (-I) 439 (0)
[M(phenM(CIO4)2’
pen WM.) 00 5.1’ 3,2k
-CFSE (kK) (,f = 1.43) 32.3 0 34,3 8-O 15.3 10.3 0
IQ?/J3* 10.3I 21.30 l9,90 24.80 21.35 17.55
-AH (kcal mole’ *)* 9.0 33,o 23,8 30,o 26,4 19.3
273 (-) 234 (0) 285 (50) 243 (6) 260 (22) 255 (15) 241 (0)
342 (-) 280 (0) 296 (14) 291 (8) 304 (19) 288 (I) 288 (0)
a(M-N) and (wo) (cm- ‘)
427 (-) 424 (0) 535 (Ill) 425 (1) 428 (3) 423 (-1) 424 (0)
556 (-) 513 (0) 562 (50) 512 (I) 512 (2) 508 (0) 508 (0)

W@bWJ421
pcr~ WM.) -. 6,2’ 5,13m
-CFSE (kK) (/= 1.28)” 0 7,l 13.7 0
239 (0) 265 (31) 265 (34) 225 (0)
v(M-N) and (wo) (cm- *) 407 (2) 411 (6)
405 (0) 405 (0)
415 (0) 422 (7) 424 (9) 415 (0)
v(M-0) and (wo) (cm- I) 553 (11) 567 (24)
538 (0) 541 (0)

- 9 . - I” ._, %_ _ - __ ,” ^ ._ _ ... _ _ - - - r-7 - II. _ L.

 S:27m 3,12’
-CFsE (kK) cf= 1.28)” 0 0 7.1 13.7 0
220 (0) 240 (0) 249 (27) 268 (45) 225 (0)
a(M-N) and (P-yg) (cmmL)
f 245 (0) 263 (0) 285 (23) ,295 (34) 260 (0)
v(MyN)
or Y(M-0) and (i”~) (cm*‘) 404 (0)P 405 (0) 410 (3) 417 (9) 410 (0)
Y(M-0) and (wO) (cm-’ ) 531 (0) 541 (0) 553 (9) 564 (19) 549 (0)
[M(&guCl)(AA)*]’ NHZQ
n 2 2 2 1
-CFSE (kK) (f = 1.28)“q 13,7 0
v(M-N) and (wO) (cm-‘) 26; (0) 2:; (3) 275 (14) 261 (0)
v(M-N) or Y(M-0) and (Y-Y@)
(cm-‘) 403 (0) 414 (7) 409 (1) 413 (0)
v(M-0) and (v-va) (cm-” ) 545 (0) 553 /3) 57s (22) 559 (0)
~r~(~~)3~

/tea WW 5,8’ 582’ 4.75’ 3‘20’

- CFSE (kK) u” = 1.2)’ 0 4.8 6,7 12.8
415 (0) 41; (0) 415 (3) 422 (9) 426 (12) 41; (0)
v(M-0) and (v-voj (crnwlY
1 537 (0) 543 (01 558 (14) 561 (16) 568 (23) 547 (0)
K[M(!WA)~1’ nH@
_...-
;t t 0 2 t 2 0
-cm3 (units off)” 0 4.OOf 5.58f lO*68f
41; (0) 418 (0) 426 (7) 429 (8) 42: i0)
v(M-0) and (wO) (cm-‘)
570 (0) 512 (1) 578 (6) 585 (13) 573 (0)

-cuss (units off)” 0 0 4.ooj 5*5&f 10.68f

r*
417 (0) 415 (0) 425 (7) 430 (1 I) 431 (9) 42: (0)
?$ v(M-0) and (P-~0) (cm-*)
3 I 562 (0) 576 (0) 579 (3) 586 (9) 592 (IS) 578 (0)
8 K[M(DBM)3I
b
-CF8E (units off)” 0 0 4.OOf S.SSf 10.68.f
ij f 362 (0) 370 (0) 376 (6) 388 (22) 390 (14) 36; (0)
‘$ v(M-0) and (V-PO)(cm-‘) 523 (0) 521 (0) 537 (11) 539 (11) 533 (2) 537 (0)
* 614 (0) 622 (0) 625 (3) 627 (5) 631 (9) 624 (0)
.c
1

F n Kef, 8. b ‘Excludingthe pairing energy. ’ Ref. 4. d Ref. 9, @Ref. 10. f Mean of doublet: 273, 288 cm”“, g Mean of doublet: 348, 361 CM-~,
_’ c Mean of doublet: 425, 442 cm-“. I Ni(II) complex = hemihydrate, J Ref. 11, k Ref. 12. 1 Ref. 7, n Ref. 13. n See text, eqn. (4). OI%(U)
$
complex. = monohy~rate, P Mean of doublet: 394,413 cm-l, 9 Assurnin~~(biq~i~~~=f(bipy), , r rUvl-0) from reb 14.
44 G.C.PERCY,D.A.THORNTON

and K,(Mox,] * 3H20 (ox = oxalate), the Co(III) compiex is diamagnetic.

However, of the 3d” complexes with n > 6, only the 38’ Ga(II1) derivatives are
generally preparatively accessibie and the CFSE order for the 3d5, 3d6 and 3d’O
species is Fe(II1) < Co(IH) > Ga(IH) whether or not Co(III) is spin-paired.
Therefore, the fact that v(M-L) foliows this order qualitatively, cannot be con-
sidered as diagnostic of spin-paired Co(JI1). In the complexes [M(N-N)s12”, the
3d6 Fe(H) derivative is also spin-paired while the 3ds Mn(II) and 3d’ Co(H) com-
plexes are preparatively accessible and spin-free. The CFSE order Mn << Fe > Co
differs from that pertaining to a series in which the three ions are spin-free,
Mn < Fe < Co. If the CF interpretation of v(M-L) shifts is valid, we expect this
difference to be evident in the v(M-N) values of these complexes.
Less predictably, the Cr(II) complexes of bipy and phen are also distinguished
by the rare spin-paired d4 configuration. Whether Cr(II) is spin-free or spin-paired,
the theoretical CFSE order is Cr > Mn. However, complexes of spin-free Cr(I1)
are usually tetragonally distorted, the additional stabilization yielding a v(M-L)
order Cr > Mn. The increased CFSE of spin-paired Cr(II) (16Dq) compared with
spin-free Cr(I1) (6Dq) should also lead to a v(M-L) order Cr > Mn.
Calculated CFSE'S are given in Table 1. These are obtained from the relation-
ships’

CFSE = -(dir,- 611,)Dg (1)

and 1ODq =fg (2)
whence CFSE = - (0.4~ -0.6n,)fg (3)
where n, and n, are the numbers of f2g and es electrons and eqn. (2) represents
Jorgensen’s factorization of 1ODq into its ligand (f) and metal ion (g) components.
AvaiIability’ of values of g for all ions represented here and values offfor (bipy), ,
(phen)3 and (AA), enables calculation of absolute values of the CFSE'S.Although
values offare not available for the ligand combinations (TFA), , (BA), , (DBM), ,
the CFSE'S of complexes of these Iigands may be obtained in units off which is a
constant for each of the series K[M(TFA),], K[M(BA),] and K[M(DBM),].
For the mixed ligand complexes [M(N-N)(AA),], f is calculated to be 1.28 from

f = 3f (N-N), +4f (AA), - (4)

Although the spectra of several of the cationic species [M(N-N)S]2+ have
been reported5*15, their re-investigation is warranted for several reasons. In earlier
work, different anions, usually halides, were present. The possibility that the
halides enter the co-ordination sphere cannot be excluded. Alkali halide pellets
were employed with attendant dangers of pressure effects, metathetical exchange
reactions between matrix halide and complex haiide and some masking of the im-
portant v(M-N) region near 250 cm-l. The Mn(I1) complexes, essential to the
present investigation as reference compounds with zero CFSE, were not studied.

J- Mol. Structure, 10 (197J)3948

CRYSTAL FIELD ASPECTS OF_ VIBRATIONAL SPECTRA. IV. 45

J
so0 LM 300 ZoQLni’ 500 Lrn 300 zmd

1 I , I II I I 1 1 I
500 LOO 300 tcmati ml Loo 300 2ami’

Fig. 1. Infrared spectra of bipy and phen complexes, 600-200 cm-‘.

The spectra of [M(phen),](CIO,)z have been reported5 but only above 600 cm-’
where no significant metal ion effects are observed.
Below 600 cm-‘, the perchlorate spectra (Fig. 1) reveal four bands with
significant metal ion sensitivity. Only the bands near 400 cm-’ correspond with
a region of Iigand absorption. Assignment of the two bands below 400 cm-’ to
v(M-N) is therefore indicated while the two metal-sensitive bands above 400 cm-’
undoubtedly have M-N character. Each of these bands exhibits a similar frequency
variation with d-orbital population of the metal ion and the shifts parallel those of
the CFSE'S.Particularly noteworthy are the appreciable shifts of v(M-N) to higher
frequency in the spectra of the Fe@) and Cr(II) complexes which are associated
with their spin-paired configuration and consistent with the discussion given above.
Fig. 2 illustrates the relationship between v(M-N) and d-orbital population
for the band of lowest frequency. The interpolation line joining the points for the
two ions of zero CFSE, Mn(I1) and Zn(II), represents the frequencies (v,) which
would be realized in the absence of CF stabilization. In general v(Zn-N) 3 v(M-N)
so that the effect on the frequencies of the ionic contraction through the series just

J. Mol. Structure, 10 (1971) 3948

 46 G. C. PERCY, D. A. THORNTON

I\/
t
-
‘i 300 l

L
T
j\/kj
3
250
Ii
.______________________~ I\

d-Orbital Population -

Fig. 2. Relationship between v(M-N), -AH, log p3 and d-orbital population forScomplexes
[M(N-N).](ClO&. The dashed line is the interpolation line yielding Y,, values. The vertical
lines in the upper diagrams represent (V--Y,&

compensates or overrides the effect of the slight increase in ionic mass. The differ-
ence (v-vo) between the observed frequencies and vO is considered to represent the
contribution to v(M-N) arising from the CFSE.
Both the stability constants (log p3) and calorimetrically determined forma-
tion enthalpies (AH) are available9 for a comparison with v(M-N). The qualitative
similarity in the trends exhibited by the three parameters (Fig. 2) is very reasonable.
Spectra-structure correlations among the Cu(II) complexes of bipy and phen
have been reported elsewhere l6 _ It suffices to mention here that the spectra yield
evidence in support of a previous suggestion3, that the relative rigidity of phen
(with a fused ring system) prevents tetragonal distortion of the Cu(E) chelate since
there is no observable splitting of the v(Cu-N) bands. Some distortion of the corre-
sponding complex of the less rigid Iigand bipy is evident from the doublet character
of v(Cu-N) but the associated Jahn-Teller stabilization is insufhcient to reverse the
frequency order..Ni > Cu predicted by crystal field theory.
The Compounds. [M(N-N)(AA)2] represent a series intermediate- between

J. Mol. S~~crure,10 (1971) 39-48

CRYSTAL FIELD ASPECTS. OF VIBRATIONAL SPECTRA. IV. 47

[M(N-N)d2+ and [M(AA),]-. Since neither bipy, phen .nor AA can span tram
positions, the mixed ligand complexes also have cis configuration’_ In %ommon
with the experience of others’, we were unabie to synthesize the Fe@) and Cu(II)
complexes. Furthermore, although biquinolyl (biquin) formed the. species
[M(biquin)(AA),], it failed to yield [M(biquin)3]2f. The spectra of
[M(N-N)(AA),] (Fig. 1) exhibit one or two metal-sensitive bands below 300 cm-‘.
Since there is no absorption in the spectra of K[M(AA),] in this region, these
bands are assigned to v(M-N) although the possibility of coupling between
v(M-N) and v(M-0) cannot be excluded. Bands near 400 cm-’ in the spectra of
MN-N)(fi),l are also present in the spectra of [M(N-N),12+ (v(M-N)) and
IM(AA), I- MM-O)), hence their assignment is uncertain. Bands near 550 cm-’
are more reliably assigned to v(M-0) by analogy with their occurrence14 in
[M(AA),]-. All four bands exhibit metal ion sensitivity which conforms with
expectations based on the CFSE’S. The fact that v(M-N) and v(M-0) follow the
same trends indicates that stabilization of the M-N bond on replacement of one

Ca
I KIM(AAl,I
I M KIMU3Al,I

Mn

FC

co
;
Ni
A..
‘.-.
Ztl
A
I , ,

600 500 COOcmi 600 500 LOOcni’

600 500 LOOmi’ ma 500 UMcmil

Fig. 3. Infrared spectra of complexes K[M(O-O)3 1, 650-350 cm-‘.

J.‘Mol. Structure, 10 (1971) 3948

48 G. C. PERCY, D. A. THORNTON

metal ion by another of higher CFSE is not accomplished at the expense of the M-O
bond stability.
For each pair of complexes [M(N-N),]‘+, [M(N-N)(AA),] (M and N-N
constant) v(M-N) is higher in the former and for each pair of complexes [M(N-N)
(AAM, IWW.l- CMconstant) v(M-0) is higher in the latter. This suggests
that the mixed ligand complexes represent an intermediate series in which the M-N
bonds are weaker than in [M(N-N)3]2t and the M-O bonds are weaker than in
CM(AA),I-.
Two or three bands are found to be significantly metal-sensitive in the spectra
(Fig. 3) of the four series of complexes K[M(O-O),] where O-O represents the
bidentate oxygen donors: AA, TFA, BA and DBM. The v(M-0) order:
Ca < Mn < Fe < Co c Ni > Zn reflects the CFSE order calculated on the
assumption of spin-free Mn(II), Fe(H) and Co(H). Magnetic moments7 confirm
spin-free configuration for these ions in the series K[M(AA),]. Generally, the band
in the range 500-600 cm-’ displays the largest shifts suggesting its assignment as
the least-coupled v(M-0). This conclusion supports 180-labelling studiesl’ on the
metal(III) acetylacetonates which have shown the band between 500 and 600 cm-’
to be far more sensitive to the heavier isotope than that near 450 cm-‘.

ACKNOWLEDGEMENTS

This work was supported by University of Cape of Town and C.S.I.R.

research grants. We thank Dr. K. G. Fiihr for the microanalyses.

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