CALCULATION

MOLECULES
OF

OF THE
BY T H E

CORRELATED

TOTAL

ENERGY

OF TWO-ELECTRON

METHOD

WAVEFUNCTIONS

I. I. O u s e i n o v ,
E . M. I m a m o v ,

T. M . M u r s a l o v ,
a n d G . M. D z h a f a r o v

UDC 539.19

The most fruitful method for calculating atomic and m o l e c u l a r s y s t e m s is the approximate H a r t r e e Fock s e l f - c o n s i s t e n t field method. This method is effective for the description of many experimental facts.
In some c a s e s , however, the magnitude of the e r r o r in calculations of the total energy is comparable with
small energy differences {energy of i n t r a m o l e c u l a r chemical bonds, the height of energy b a r r i e r s , potentials
of i n t e r m o l e c u l a r interactions, excitation energies, etc.). Thus theoretical estimates of all these observed
quantities are not unambiguous if allowance is not made for electron c o r r e l a t i o n in the calculations [1, 2].
The most effective method for taking account of c o r r e l a t i o n between electrons is the method of c o r r e lated wavefunctions. In this method, use is made of the so-called c o r r e l a t e d wavefunctions, which depend explicitly on the i n t e r e l e c t r o n i c distances. One of the possibilities of changing f r o m the H a r t r e e - F o c k approxi9 mation for a n N - e l e c t r o n s y s t e m to a wavefunetion c o r r e l a t e d in this way involves multiplication by a c o r r e lation f a c t o r [3, 4].
The p r e s e n t p a p e r examines the calculation of the total energy of t w o - e l e c t r o n molecules by means of
the c o r r e l a t e d wavefunctton.
The c o r r e l a t e d wavefunction of a t w o - e l e c t r o n molecule can be r e p r e s e n t e d in the f o r m

9 <Xl,

(xl,

(1)

where x i denotes the set of spatial and spin coordinates of the i - t h e l e c t r o n (i = 1, 2), ri2 is the distance between
the electrons, r
x2) is the determinant wavefunctioa of the molecule in the H a r t r e e - - F o c k approximation,
and C~p r e p r e s e n t s p a r a m e t e r s determined f r o m the condition for a total energy minimum.
By introducing the symbols
p P *~j

~'= 2 ~p

p,

~ + ~~
pp,

%,~+~',
.P

(3)

we can readily obtain the following e x p r e s s i o n for the total energy of the t w o - e l e c t r o n molecule:
f (~)0'~(])0~T1 tiT2

n ZqZ,

(4)

1/2
2 dxJyldz i,
cri is
6/=--1/2
is the spin coordinate of the i-th electron, Zq is the charge of the q-th nucleus, and Rq/ is the distance between
the q-th a n d / - t h nuclei.
where H i s the e l e c t r o n i c p a r t of the nonrelativistie Hamiltonian of the molecule, d~i =

Thus the total e n e r g y of the t w o - e l e c t r o n molecule E is expressed in t e r m s of the m a t r i x elements of

the o p e r a t o r s ]~ and h between the determinant wavefunctions r
It can be seen f r o m Eqs. (2) and (3) that the
o p e r a t o r s M and h a r e s y m m e t r i c a l with r e s p e c t to permutation of the coordinates of the electrons, so that we
can use the t h e o r e m of the m a t r i x elements of s y m m e t r i c a l o p e r a t o r s between determinant wavefunctions [5].
Thus by applying this t h e o r e m to Eq. (4), c a r r y i n g out the summation with r e s p e c t to the spin coordinates of
the electrons, and assuming that the m o l e c u l a r orbitals are r e p r e s e n t e d in the f o r m of linear co,mbinations
of atomic orbitals of the Slater type, we obtain finally for the m a t r i x elements of the o p e r a t o r s h and M the
expressions :
S. M. Kirov Azerbaidzhan State University, Baku. T r a n s l a t e d f r o m Zhurnal Strukturnoi Khimii, Vol. 20,
No. 6, pp. 1129-1131, N o v e m b e r - D e c e m b e r , 1979. Original article submitted November 9, 1978.

0022-4766/79/2006-0965507.50 9 1980 Plenum Publishing Corporation

965

p Pijhl

pp" P

ijhl

h l\

rp

@ V oc ~p, Z cic.c Cz~

p2a' p

#hz 3 h t

2 ( p P+

P"
P')(ij]r~l+2p ' ( V ~ @V~)]kl) 2(pq-p')

,9//1

"~

(lrl[rPl~P'

(VI + V~) I i]) "

rP+P'-I

kl~

pp" ( i ] [ r P l ; P ' - 2 l k l ) - -

(6)

where
(i]l~l~Z)

S~ti(f >Q(2)/~(t)X~(2)dqdv2,

(7)

E~ 1 is the total e l e c t r o n i c energy of the molecule in the H a r t r e e - F o c k - R o o t h a a n approximation, Xp--- (np/pmp)

a r e r e a l atomic orbitals of the Slater type, c s r e p r e s e n t s the coefficients of the l i n e a r combination of atomic
o r b i t a l s , and rqi is the distance f r o m the ith e l e c t r o n to the qth nucleus.
In the derivation of Eq. (6) we used Eq. (14) f r o m [6].
It can be seen f r o m Eqs. (4), (5), and (6) that the total energy of t w o - e l e c t r o n molecules, calculated using
the c o r r e l a t e d wavefunction (1), is e x p r e s s e d in t e r m s of the m o l e c u l a r integrals with c o r r e l a t i o n factor rk2
(k> - 1 ) , containing atomic orbitals of the Slater type. It should br e m p h a s i z e d that the t h r e e - and f o u r - c e n t e r
integrals encountered in Eqs. (5) and (6) can be e x p r e s s e d in t e r m s of one- o r t w o - c e n t e r i n t e g r a l s with the
c o r r e l a t i o n f a c t o r rk2. F o r this p u r p o s e it is n e c e s s a r y to use the equation for the expansion of orbitals of the
Slater type about a point "displaced f r o m the orbital c e n t e r [7]. F o r o n e - and t w o - c e n t e r i n t e g r a l s with the c o r relation f a c t o r r ~ (k > - 1) containing atomic orbitals of the Slater type, g e n e r a l analytical equations have been
obtained f o r all types of i n t e g r a l s of this kind in [8-12].
As an example of the application of the analytical equations obtained in [8-12] for one- and t w o - c e n t e r
c o r r e l a t i o n i n t e g r a l s , we calculated the total e n e r g y of the ground state of the helium hydride ion Hell + using
the c o r r e l a t e d wavefunction
= (l + ~,1~)o0,

(8)

w h e r e ~0 is the d e t e r m i n a n t wavefunction of the ground state of Hell + in the H a r t r e e - F o c k - R o o t h a a n a p p r o x i raation, compiled using the Starer functions given in [13] and t h e i r coefficients in the l i n e a r combination.
The calculation of the total energy of the ground state of Hell + was c a r r i e d out using Eqs. (4), (5), and
(6) on the BESM-6 c o m p u t e r of the Institute of C y b e r n e t i c s of the Academy of Sciences of the Azerbaldzhan
SSR using p r o g r a m s written in ALGOL-60 for calculating all the one- and t w o - c e n t e r integrals encountered
with c o r r e l a t i o n f a c t o r r k, containing a t o m i c orbitals of the Slater type.
The calculations f o r the total energy of the ground state gave the value -2.968302 atomic unit (it may be
noted that the total e n e r g y of the ground state of Hell + in the H a r t r e e - F o c k - R o o t a a n approximation i s - 2 . 9 3 3 1 2 6
atomic unit, and the equilibrium i n t e r n u c l e a r distance R = 1.455 atomic unit [13]). The value of the p a r a m e t e r
a = 0.25 was d e t e r m i n e d f r o m the condition f o r a m i n i m u m total energy. Thus allowance f o r c o r r e l a t i o n between the e l e c t r o n s by m e a n s of the c o r r e l a t e d wavefunctton (8) i m p r o v e d the total e n e r g y of the ground state
of Hell+ by AE =E--E0 = -0.035176 a t o m i c unit, which amounts to 1.2% of the total e n e r g y E0 in the H a r t r e e Fock-Roothaan approximation.
In addition, we d e t e r m i n e d the d i s s o c i a t i o n e n e r g y of Hell +, which was found to be equal to 1.757 eV. It
m a y be noted that this value of the d i s s o c i a t i o n e n e r g y shows good a g r e e m e n t with the e x p e r i m e n t a l value of
1.79 eV [14]. It should be emphasized that in the determination of the d i s s o c i a t i o n energy we used the m o s t
a c c u r a t e published value of the total e n e r g y of the helium atom, equal to - 2 . 9 0 3 7 2 4 a t o m i c unit [15].

LITERATURE

1.
2.
3.
4.
5.
6.

966

P.
W.
R.
P.
H.
W.

CITED

O. L6wdin, Adv. Chem. Phys., 14, 283 (1969).

Kutzelnigg, Top. C u r r . Chem., 41, 31 (1973).
J a s t r o v , Phys. Rev., 98, 1479 (1955).
O. L0wdin, Rev. Mod. Phys., 32, 328 (1960).
A. Bethe, Quantum Mechanics, Springer-Verlag (1957).
Kolos and C. C. J. Roothaan, Rev. Mod. Phys., 32, 219 (1960).

7o

8,
9.
10.
11.
12,
13.
14.
15.

I. [. Guseinov, J. Chem. Phys., 69, 4990 (1978).

I. I. Guseinov and T. M. Mursalov, Zh. Strukt. Khim., 15,956 (1974).
I. I. Guseinov, T. M. Mursalov, and E. M. I m a m o v , Zh. Strukt. Khim., 16, 1066 (1975).
I. I. Guseinov, T. M. Mursalov, and E. M. I m a m o v , Zh, Strukt. Khim., 1.77, 728 (1976).
I. I. Guseinov and T. M. Mursalov, Zh. Strukt. Khim., 17, 1117 (1976).
I. I. Guseinov and T. M. Mursalov, Zh. Strukt. Khim., 17..._, 1119 (1976).
P. E. Cade and W. Huo, Atomic Data and Nuclear Data T a b l e s , 12, 415 (1973).
W, Kaul, U. L a u t e r b a c h , and R. Taubert, Z. Naturforsch., 16_..~a, 624 (1961).
T. S. Carlton, J. C h e m . Phys., 5__3, 4234 (1970).

NMR SPECTRA
DETECTED
FOR

OF

FROM

SHORT-LIVED
THE

RADIOFREQUENCY
R. Z. Sagdeev,
A. Z. Gogolev,
A. G. Semenov,

CPN

FREE

RADICALS,

EFFECTS

PUMPING
Y u . A. G r i s h i n ,
A. V. Dushkia,
a n d Y u . N. M o l i n

UDC 541.139

Existing methods for o b s e r v i n g the NMR s p e c t r a of f r e e r a d i c a l s in solutions a r e applicable only for

stable r a d i c a l s at high concentrations [1]. The p r e s e n t p a p e r gives for the f i r s t t i m e a method for recording
the NMR s p e c t r a of s h o r t - l i v e d f r e e r a d i c a l s . A n e c e s s a r y condition for the r e a l i z a t i o n of this method is the
o b s e r v a t i o n (in the c o u r s e of the r a d i c a l p r o c e s s ) of the effects of c h e m i c a l p o l a r i z a t i o n of the nuclei (CPN)
in the r e a c t i o n products outside the cage. This l a s t f e a t u r e m e a n s that the i n t e r m e d i a t e f r e e r a d i c a l s R, pol a r i z e d as a r e s u l t of s i n g l e t - t r i p l e t t r a n s i t i o n s in radical p a i r s , have a sufficiently s h o r t lifetime T for the
n u c l e a r p o l a r i z a t i o n to be p r e s e r v e d at the m o m e n t of f o r m a t i o n of the final r e a c t i o n products (for example
of the type RX). If in t i m e ~- the s a t u r a t i o n of the r e s o n a n c e t r a n s i t i o n s in the NMR s p e c t r u m of the i n t e r mediate r a d i c a l R is c a r r i e d out, the i n t e n s i t y of the corresponding p o l a r i z e d signals in the NMR s p e c t r u m
of the final r e a c t i o n products changes. Thus the dependence of the intensity of the C P N on the frequency of
the s a t u r a t i n g r a d i o f r e q u e n c y (RF) field will r e p r e s e n t the NMR s p e c t r u m of the i n t e r m e d i a t e radical.
It should be noted that t h e r e is a definite analogy between the p r o p o s e d method and the f a m i l i a r ENDOR
method: In both c a s e s the nuclear r e s o n a n c e t r a n s i t i o n s in the f r e e r a d i c a l s a r e s a t u r a t e d . In c o n t r a s t to the
ENDOR method, however, the proposed method detects not the intensity of the ESR signals of the r a d i c a l s but
the CPN effects in the NM_R s p e c t r u m of the d i a m a g n e t i c r e a c t i o n p r o d u c t s . This l a s t f e a t u r e also m a k e s it
possible to r e c o r d the NMR s p e c t r a of s h o r t - l i v e d f r e e r a d i c a l s .
We can c o n s i d e r the values of the f r e q u e n c y w 2 and amplitude H2 of the saturating R F field. The value of
w 2 is d e t e r m i n e d by the working f r e q u e n c y of the NMR s p e c t r o m e t e r ~00 and the H F I constant ai in the r a d i c a l s
(typical values of ai f o r alkyl r a d i c a l s a r e 30-90 MHz). The NMR s p e c t r u m for each group of equivalent nuclei
in the r a d i c a l is a doublet with f r e q u e n c i e s ~ 0 - a i / 2 and co0 + a i / 2 . Since the two signals a r e s y m m e t r i c a l with
r e s p e c t to the f r e q u e n c y w0, it is sufficient in p r i n c i p l e to o b s e r v e only one signal (for example with ~ 0 - ai/2)
f o r each group of equivalent nuclei in the i n t e r m e d i a t e r a d i c a l . The need to o b s e r v e the nuclear p o l a r i z a t i o n in
the r e a c t i o n p r o d u c t outside the cage and to s a t u r a t e the n u c l e a r t r a n s i t i o n s in the r a d i c a l during its lifetime
obviously lead to the inequality (TnH2)-l<~- < Tn, w h e r e T n is the n u c l e a r 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 the
radical. The known values of T n in the r a d i c a l s lie in t h e r a n g e 10-3-10 -5 f r o m [2]. F r o m this it follows that
to c a r r y out the e x p e r i m e n t s it is sufficient that H2( 10-100 Oe.
The p r o p o s e d method was verified e x p e r i m e n t a l l y for the c a s e of benzyl r a d i c a l s , g e n e r a t e d by the photol y s i s of dibenzyl ketone using a DRSh-500 m e r c u r y lamp d i r e c t l y in the d e t e c t o r of a h i g h - r e s o l u t i o n BS-487C
(Tsela) NMR s p e c t r o m e t e r with a working f r e q u e n c y of 80 MHz. We o b s e r v e d the signal of the CH 2 protons of
the r e a c t i o n product outside the cage, dibenzyl, which was positively p o l a r i z e d [3]. When an RF field was
applied to the individual coils in the d e t e c t o r f r o m a specially constructed g e n e r a t o r (w 230-60 MHz, H 2 ~15 Oe),
Institute of Chemical Kinetics and Combustion, Siberian Branch, A c a d e m y of Sciences of the USSR. T r a n s lated f r o m Zhurnal Strukturnoi Khimii, Vol. 20, No. 6, pp. 1132-1133, N o v e m b e r - D e c e m b e r , 1979. Original
a r t i c l e submitted August 10, 1979.
0022-4766/79/2006-0967507.50

9 1980 Plenum Publishing C o r p o r a t i o n

967