244

Ab Initio Calculation of Spin-Orbit Interaction in

Polyatomic Molecules Using Gaussian-Type
Wavefunctions

Jacques Breulet*
Laboratoire de Chimie Physique Mol&culaire,CP.160, Uniuersitk Libre de Bruxelles, Aue. F.D. Rooseuelt, 50, B-1050
Brussels, Belgium
Received 23 July, 1980; accepted 18 November, 1980

A set of programs has been developed to calculate molecular spin-orbit interaction with Gaussian-type
wavefunctions in connection with the popular GAUSSIAN 76 program. The spin-orbit contributions
to the fine structure of 0 2 (X3L\g),NH ( X 3 2 - ) ,and CH2 (X3B1)are evaluated with the standard STO-
3G and 6-31G basis sets; for NH the influence of bond functions added to the latter basis set is also in-
vestigated. The results are compared to values previously obtained with other types of basis sets.

I. INTRODUCTION action in these molecules is quite small and not

sufficiently dominant in the fine-structure pa-
For a few years it has been possible to perform
rameters to neglect the spin-spin interaction,
ab initio calculations of fine-structure parameters
which is not calculated here. However, for the
using Gaussian (GTO) and Gaussian-lobe (GLO)
polyatomic systems mentioned above in which
basis functions. Very elaborate calculations have
there occurs an intersystem crossing, this is no
been carried out for diatomic molecules like 0 2 , l
longer the case as will be apparent later. The
NH,2 and polyatomic molecules like CH2,3 and
present calculations should thus be considered as
H2C0.4
test cases.
Our previous work dealt with the dissociation
From this point of view and among other things,
process of the molecule NH-N2 in its ground
we also compare here the quality of GTO basis
state.5The dissociation paths of this molecule and
functions with that of Gaussian-lobe and Slater-
other isoelectronic systems like CH2N2,6 NzO, etc.,
type functions. Also the incidence of adding bond
are characterized by a singlet-triplet intersystem
functions to a double-zeta basis set is investigated
crossing, and hence in order to study the resulting
in the case of NH.
“forbidden transitions” it was necessary to develop
a set of programs able to calculate the spin-orbit
interaction in conjunction with the popular SCF 11. THEORY
GAUSSIAN 76 p r ~ g r a mwhich,~ was used to cal-
culate the wavefunctions of these systems. A. Spin-Orbit Coupling
It seemed that it would be interesting to present
results obtained with our method for the spin- In molecules, the spin-orbit coupling can be
orbit part of the fine-structure parameters for the described by the spin-orbit part of the Breit-Pauli
molecules 0 2 ( X 3 2 g ) , NH ( X 3 2 - ) , and CH2 Hamiltonian8:
(X3B1).
As the results will show, the spin-orbit inter-

* Aspirant d u Fonds National Belge de la Recherche

Scientifique.

Journal of Computational Chemistry,Vol. 2, No. 3,244-250 (1981)

0 1981 by John Wiley & Sons, Inc. CCC 0192-8651/8l/030244-07$01.40
Polyatomic Molecules 245

where a refers to nuclei and i and j to electrons.
The first term represents the so-called “spin-same
orbit” interaction, i.e., the interaction between the
spin angular momentum and the field of the nuc-
lei; the second one describes the “spin-ther orbit”
interaction, i.e., the mutual interaction between
the spin and the orbital angular momenta of
electrons. An alternative and more useful form of
the same equation will be used here:
Hso = Hsso + Hsoo
spin-other orbit integrals to electronic repulsion
integrals. This makes it possible to use classical
SCF integral computer programs to evaluate the
spin-orbit integrals. One finds easily from eqs. (1)
and (2) that
( @i ( l ) @ i ( l )IL1(2)I* j ( 2 ) @ k (2))
) [k ( 2 ) @ k ( 2 ) ) = 0
= ( @ i ( 1 ) @ j ( 1 ) l L 2 ( 1@ (3)
( @ i ( l ) @ j ( lIL’(2)
) [ @i(2)@j(2))
= ( @ i ( l ) @ j ( l ) l L 2 ( 1I @
) i ( 2 ) @ j ( Z ) ) (4)

where The latter two relations considerably reduce the

number of integrals to be calculated.

Hsoo = - C
. . [ZLi(j) + Lj(i)]S(i)/rt B. Zero-Field Splitting
1J
As has been proposed in Sec. I, we will calculate
L i(j) is the orbital angular momentum of particle here the spin-orbit part of the fine-structure pa-
j about the ith particle and S ( i )is the spin oper- rameters of the molecules 0 2 , N H , and ClH2. Ex-
a t o r ~We
. ~ shall also use the notation: perimentally, the transitions between the spin
Q1(2) = L’(2) + 2L2(1) levels of a given triplet state are often related to
two independent parameters D and E that can be
which allows us to rewrite the Hsoo operator in the connected to the theory by the use of the tensor
compact form: components of the spin-spin ( H s s )and the spin-
HSOO= Q’(2) + Q2(1) orbit (Hso) operators.s Both D and E contain
spin-spin and spin-orbit contributions:
A very general derivationlo allows us to write for
any set of functions @i and for the z Cartesian D = Dso + Dss
component, for example, E = Eso + Ess
( @pi (1)JL I @j ( 1 )) and the states that contribute to either parameter
are determined by symmetry considerations. For
diatomic molecules, for example, the only nonzero
matrix elements are those connected to the z -in-
ternuclear axis and therefore E is zero.
Since for light atoms the spin-orbit interaction,
as well as spin-spin interaction, which is not
treated here, is a small perturbation of the Born-
Oppenheimer Hamiltonian, one can use pertur-
bation theory to evaluate the fine-structure pa-
rameters D and E.8
The spin-spin interaction will appear to first
order of perturbation and for those triplet states
with an analogous form for that are orbitally degenerate there will also appear
a spin-orbit contribution, the so-called “spin-orbit
(1)ILf(l)l@ k ( 2 ) @ ) 1 ( 2 ) )
(@pi(l)@p, coupling” (SOC) constant to the same order. The
In other words, the spin-same orbit integrals can nondiagonal spin-orbit interaction, which is not
be reduced to nuclear field integrals and the negligible, contributes to second order.
246 Breulet

Since we are concerned with orbitally nonde- IV. SPIN-ORBIT MATRIX ELEMENTS
generate triplet states 3'kk,i,i.e., 3Z;of 0 2 , 3 2 - of
NH, and 3B1 of CH2, the first-order spin-orbit A. 0 2 a n d N H
interaction is absent. The splitting of the spin
levels is given by the secular equation It has been demonstrated by Langhoffl for 0 2
and Palmiere and Sink2for NH that the dominant
interaction with the triplet ground state in these
U1,l - a1,o Ul,-l,
molecules is due almost exclusively to the first
ao,1 ao,o - ao,-1 =0 (5) Hso-active singlet state. This property was ex-
a-1,1 a-1,o U-l,-l -x plained on the basis of two facts: (1)the large de-
nominator that appears for higher states in the
second-order perturbation expansion; and (2) the
cancellation of other upper contributions. We shall
then retain only the following matrix elements:
-(1Z+IHso132;) for NH

The roots of eq. (6) give the energies of the three -(12iIHso132;) for 0 2

substates: The lowest configuration of NH is

3 E k , i = 3 E k -k xi (7) ( 1a)2( 2 0 ) ~3( ~ )1 ~ ~
( ) ~ (8)
We will be concerned here with the Hso part of eq. giving rise to the three states and eigenfunctions
(6).

111. PROGRAMS, BASIS SETS

The SCF energies and wavefunctions were ob- 1
tained with the well-known program GAUSSIAN *('2+)= 21/2(1. .(17r+)(G-)I-l..
.(K-+)(l*-)I)
76 for closed-shellstructures, and with the method
However, since the program GAUSSIAN 76
of Davidson (0CBSE)ll coded by Morokuma and
does not generate imaginary molecular orbitals, we
IwataI2 for open-shell structures. The atomic
had to define new eigenfunctions in terms of the
spin-orbit mono- and bielectronic integrals were
Cartesian orbitals 7 r x and 7 r y . We showed else-
obtained with a revised version of the integral
where5 that
package links of GAUSSIAN 76. The molecular
spin-orbit integrals were calculated with a revised
version of a molecular integral transformation
program.13 Calculations were made with two basis
is sufficient to describe adequately the lA state. In
sets built into GAUSSIAN 76: the minimal STO-
a similar way, we define the following wavefunc-
3G14 and the double-zeta quality 6-31G15 basis
tions:
sets. Since the derivative of a d function gives p
and f functions, spin-orbit integrals over a polar-
ized basis set cannot be calculated with GAUSS-
IAN 76. An alternative solution to the addition of
polarization to the basis functions is the use of
bond functions. The bond functions we used for
NH are four ( s ,p,, pr, p,) single Gaussian func-
tions of exponent 0.8 located near the H atom a t
0.1 of the bond length. These characteristics have
been proposed by Neisius and Verhaegen.16
Polyatomic Molecules 247

and taking into account the fact that the operators component corresponds to the Y Cartesian part of
considered here itre spin-dependent, one obtains the spin-orbit operator, or in other words, to a
easily for the z component, for example, rotation around the Y axis (fly).

The nonvanishing contributions of the spin part

correspond to the triplet components M.9 = f 1.
One then obtains

+ I (1A1,2lH&J%)
If xx and ry are orbitally degenerate
(SxxIHsoIT) = (SyyIHsolT> (13)
WA1,2) -

The 3B1 state is described by the determinantal

1-
E(3B1)
12

One can then write, with the definitions (9)- function

(11): 'I'(3B I
= ( l a 1)2(2ad2(1b d2(3a 1 (1 1 I
( 12+I Hso I"Z,) = 2 q s,, I Hso I T )
One then finds
(1L11HS013ZJ = 0 (14) 1
A completely analogous derivation can be carried (XIHsYol3Bd = - 7(3allLy(l)llbl)
21
out for 0 2 .
+ -(2i1 3a13al IL; (1)I3a l l b l )

+ T11 ( ( l U 1 . . .lb2)(la1.. .lb2)lL;(1)13allbl)

B. CH:!
The case of CH2 is a little more complicated.
First, it is well known17that two configurations are
needed to describe correctly the first l A l excited
state (symmetry group CzO).These two configu-
rations are
9 ( X ) = I (la1)2(2a1)2(lb2)2(3u1)2)
9 ( Y ) = I (la1)2(2a1)2(lb~)(16,)21
A CI calculation gives the two following states:
'I'('A1,l) = a"(X) + b\k(Y)
'P(lA1,2) = b \ k ( X ) - a'I'(Y)
Both will be taken into account. With the help of
group theory, one can find that these states will
interact with the fundamental 3R1 state through
the R1 component of the spin-orbit operator. In
the axis convention shown below the B1 active
3
-- ( ( l a l . . .lb2)3allL-k(2)
2i
+ L;(l)llbl(lal.. .lb2))
The matrix elements ( YIH&13Bl) are of course
identical except that (3~13allL~(1)13allbl) is
replaced by (lbllbllL~(1)13allbl). According to
L a n g h ~ f fother
, ~ upper states do not contribute
significantly either to Dso or to Eso.
V. USE OF "COMMON" A N D
"INTERMEDIATE" HAMILTONIANS
For NH and 02, we generated our wavefunctions
by a Fock matrix corresponding to the
X 3 2 - ( X 3 Z ; ) structure, which ensures a K , - 7ry
(xu,- 7 r u y ) degeneracy. This procedure provided
us with orthonormal sets of molecular orbitals.
248 Breulet

Table I. Comparison of spin-orbit mono- and bielectronic contributions by symmetry blocks in different basis sets for
0 2 (cm-1).

Basis set
Type Min. S T O ~ Min. GLOa STO-3Gb DZ-STOa DZ-GLOa 6-31Gb

( 4Hssolr ) -209.53 -192.43 -174.42 -285.05 -275.48 -261.53

(rrlHsool@@) 50.32 48.51 44.25 59.29 57.59 57.12
( *@I Hsoolra) 31.34 28.99 24.04 44.33 43.09 39.63
(rrlH s o o l r r ) -2.11 -2.02 3.28 -2.45 -2.20 2.98
Total -129.98 -116.95 -102.85 -184.88 -177. -161.8
a See ref. 1.
This work.

Other work having shown that the wavefunctions
of both *2+(lZ;) and 3Z-(32;) states are de-
scribed quite correctly by these molecular orbit-
als,18 we avoided the use of a rather tedious
nonorthogonal formalism.
Concerning CH2, the orbitals of \ k ( X )and \k( Y )
were simultaneously described by means of the 3B1
Hamiltonian, considered as a “common” Hamil-
tonian. Moreover, the molecular integrals of the
3B1state were used to carry out the CI calculation
between the two singlet configurations. This use
of an “intermediate” Hamiltonian in a CI calcu-
lation has been tested successfully by Lievin and
Verhaegen.6
VI. RESULTS AND DISCUSSION
A. Calculated Values of Dso for NH, 0 2 , and
CH2
Previous workls has shown the validity of the
use of GLO and GTO basis sets for the calculation
of spin-orbit integrals, particulary with respect to
the results obtained with Slater-type basis sets.
Tables I and I1 show the results of spin-orbit
integrals regrouped into symmetry blocks for 0 2
and NH, respectively. Our values are compared to
those previously obtained with minimal and dou-
ble-zeta quality GLO or GTO basis sets. Several
conclusions can be drawn. First, it is obvious that
our minimal and double-zeta STO-3G and 6-31G
basis sets give entirely similar results to those
obtained with other basis sets of the same quality.
Only the value of the ( T ~I Hso
T IT T )block is quite
different in our work in the case of 0 2 . This is be-
cause some integrals that Langhoff found to be
negative were nearly zero in our calculation. The
results are with respect to this similarity not sur-
prising, i.e., a minimal basis set fails completely to
describe the spin-orbit interaction while an ex-
tended one gives satisfactory results. Second, the
results of the 6-31G + BF basis set for NH show
that the introduction of a bond function (BF) is not
useful. This is not surprising either since the
spin-orbit interaction concerns essentially the
region of space located near the nucleus and hence
the inner orbitals. In Table 111, our calculated
values of Dso for 0 2 and NH are compared to the

Table 11. Comparison of spin-orbit mono- and bielectronic contributions by symmetry blocks in different basis sets
for NH (cm-I). ~ ~~ ~~

Basis set
Type STO-3Ga DZ-STO~ DZ-GTO~ 6-31Ga 6-31G -t BFa

( rIHssol r) -97.21 -120.27 -118.24 -123.18 -125.31

( rr I Hsoo I a@> 27.22 29.83 29.24 29.28 31.54
(X@IHsool ru) 19.06 21.85 21.73 21.26 22.85
(rrlHsool7rr) -1.27 -1.15 -1.09 -1.11 -1.22
Total -52.2 -69.74 -68.36 -73.75 -72.14
a This work.
b See ref. 2.
 Polyatomic Molecules 249

Table 111. Dso values obtained in different basis sets for 0 2 and NH. Comparison with other work and experiment.

I (SIHsoln l2 AE(S - T)a Dso Dssb D Dexpt

Mol. Basis set (cm-2) (cm-l) (cm-') (cm-1) (cm-1) (cm-l)
NH STO-3G 2725 21,200 0.13 1.60 1.73 1.856
6-31G 5439 21,200 0.26 1.60 1.86 1.856
(ref. 21)
6-31G + BF 5204 21,200 0.25 1.60 1.85 1.856
GTOC - - 0.27 1.62 1.89 1.856
STOd 0.28 1.92 2.20 1.856
0 2 STO-3G 10,580 13,195 0.80 1.55 2.35 3.965
(ref. 22)
6-31G 26,177 13,195 1.98 1.55 3.53 3.965
(; LOe - - 2.40 1.45 3.85 3.965
aExperimental values have been used here.
%ee text for D s ~values
; used here.
'Includes contributions of 311 and lII states (ref. 2).
dCI calculation with DZ-STO basis set (ref. 2).
e C ~calculation with DZ-POL basis set (ref. 7).

best available data in the literature. Two prelim-
inary remarks should be made. First, the singlet-
triplet term energies used for the calculation of
Dso are the corresponding experimental values
since it is well known that the calculated term
energies are too large and thus would give Dso
values that are too small. Second, Dss was not
calculated here, but a compilation of the literature
for 0 2 (ref. 19) and NH (refs. 2 and 20) leads us to
believe that Dss(NH) = 1.6 cm-l and Dss(0Z) =
1.55 cm-I are quite accurate values. Since Dss is
nearly constant from one basis set to another,lgthe
comparison of D calculated with D experimental
made in Table 111 gives a good idea of the validity
of our calculations for Dso. It appears clearly that
Table IV. Dso values obtained for CH2 with 6-31G
comDared with Lannhoff's.
'A1.l 10,609 6-31G 58
DZPb 64
'A1,2 38,338 6-31G 163
r)zpb 206
DSO total 6-31G = 0.020 cm-'
DZP = 0.023 cm-'
a a and b coefficients (see text) are 0.963 and -0.269 in
6-31G basis set and 0.94 and -0.26 in DZP basis set.
[' Reference 3.
the calculation using only one interacting state
together with the 6-31G basis set leads to results
nearly as accurate as those obtained after very
elaborate procedures.
An entirely similar conclusion can be drawn
from Table IV, where we have compared for CH2
the Dso(6-31G) values with the DSO(DZP) ones.
Although DSO is really negligible with respect to
Dss(0.784 ~ m - l ) it
, ~seemed worthwhile to make
such a calculation for one of the smallest poly-
atomic molecules.
B. Use of GTO Basis Set in the Intersystem
Crossing Problem
One could object that, in the preceding section,
Dss was not calculated while Dso is not dominant
in D . However, our aim is to calculate the splitting
of the spin levels a t intersystem crossing points.
Since a t these points, the triplet and singlet states
become degenerate in the nonrelativistic approx-
imation, the denominator in eq. (6) is zero and
0.011
0.012
perturbation theory in the nondegenerate limiting
0.009 case is no longer valid. One has to diagonalize the
0.011 corresponding interaction matrix. In this matrix,
the spin-spin elements will be completely negli-
gible with respect to the spin-orbit ones that are
roughly 100 times bigger (see Table 111,where Dss
= (3*lHss13*) = 1.6 cm-' and Table 11:
(3\Iilffso11\k)~.31~ = 160 cm-l). That explains
250
why the present work is devoted to the calculation
of spin-orbit matrix elements only.
CONCLUSION
We have developed a set of programs in con-
junction with GAUSSIAN 76 to calculate the
spin-orbit part of the fine-structure parameters
of the molecules 02, NH, and CHZ. We have shown
that it is possible with minimum effort and with
the basis sets built into GAUSSIAN 76 to ap-
proach the experimental values of this property.
We think that this method could be used for the
calculation of spin-orbit interaction at intersystem
crossing points in larger molecules such as NzO,
NBH, and CHZN2. This last point will be treated
in a future article.
The author is very grateful to Professor G. Verhaegen
and Dr. J. Lievin for many helpful comments throughout
the course of this work.
References
1. S. R. Langhoff, J . Chem. Phys., 61,1708 (1974).
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(1976).
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Breulet
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