SLATER SCREENING CONSTANTS IN ATOMIC AND MOLECULAR ORBITALS*

by

J. 0. H i r s c h f e l d e r and A . C . Wahl
The U n i v e r s i t y of Wisconsin T h e o r e t i c a l Chemistry I n s t i t u t e
Mad i son, W i s c ons i n

T h i s r e s e a r c h w a s supported by t h e f o l l o w i n g g r a n t : N a t i o n a l
A e r o n a u t i c s and Space A d m i n i s t r a t i o n Grant NsG-275-62.

I. INTRODUCTION

(930)
S l a t e r s c r e e n i n g c o n s t a n t s and S l a t e r o r b i t a l s

/ have enabled

a whole g e n e r a t i o n of chemists and p h y s i c i s t s t o c a l c u l a t e approximate

v a l u e s of many of t h e p h y s i c a l p r o p e r t i e s of atoms.

The use of

s c r e e n i n g c o n s t a n t s i m p l i e s t h a t a n atomic o r b i t a l corresponding t o
a g i v e n s e t of e l e c t r o n i c quantum numbers i s t h e same, e x c e p t f o r
a uniform s c a l i n g of the c o o r d i n a t e s , q u i t e i r r e s p e c t i v e of which

atom or i o n i s under c o n s i d e r a t i o n .

T h i s concept of i n t e r c h a n g e a b i l i t y

of o r b i t a l s h a s g r e a t l y s i m p l i f i e d our mental p i c t u r e of atomic

structure

An adequate simple model of a molecular o r b i t a l c e r t a i n l y must

be more complicated t h a n a S l a t e r atomic o r b i t a l .

The molecular

o r b i t a l s v a r y i n s i z e and shape a s t h e i n t e r n u c l e a r s e p a r a t i o n s a r e
changed.

N e v e r t h e l e s s , as chemists we f e e l c o n f i d e n t t h a t i s must

be p o s s i b l e t o develop t h e concept of i n t e r c h a n g e a b i l i t y of molecular

o r b i t a l s on some s o r t of corresponding s t a t e s b a s i s .

We a r e

impressed w i t h t h e simple r e g u l a r i t i e s which c h a r a c t e r i z e most

molecules:

t h e a d d i t i v i t y of bond e n e r g i e s ; t h e a c c u r a t e

r e p r o d u c i b i l i t y of bond l e n g t h s , bond a n g l e s , and bond f o r c e

constants; etc.

A s our t h e o r e t i c a l t r e a t m e n t s and mathematical e x p e r i m e n t a t i o n

g i v e p r o g r e s s i v e l y c l o s e r analogues t o n a t u r a l phenomena, i t i s
e v i d e n t t h a t two t y p e s of t h e o r i e s w i l l emerge.

F i r s t , due t o

t h e development of computers capable of remembering and manipulating

v e r y g r e a t d e t a i l , t h e r e w i l l be t h s higk.ly complex f o r m u l a t i o n s
.

r e p r e s e n t i n g numerical models of p h y s i c a l systems which can be

a s s i m i l a t e d o n l y by t h e high speed computing machines which generated
them.

And second, t h e r e w i l l be t h e s l x p l i f i e d s e m i - e m p i r i c a l

formulations which t h e human mind can comprehend and manipulate i n

a s o p h i s t i c a t e d c o n c e p t u a l o r a n a l y t i c a l manner.

The computing

machines w i l l provide s p e c i f i c answers t o s p e c i f i c q u e s t i o n s i n much

t h e same manner a s t h e r e s u l t s of l a b o r a t o r y experiments.

However,

t h e r e i s a g r e a t need f o r t h e o u t p u t of t h e computing machines

d e s c r i b i n g t h e s e "numeric systems" t o be i n an a c c e s s i b l e and u s a b l e
form.

These simplified r e p r e s e n t a t i o n s w i l l h e l p t h e s c i e n t i s t t o

s e e t h e important f e a t u r e s of t h e model and make i t e a s i e r f o r him

t o develop a simple concept or u n d e r s t a n d i n g of t h e phenomena.

The'

s c i e n t i s t w i l l then make q u a n t i t a t i v e d e f i n i t i o n s of t h e important

f e a t u r e s and u s e the numerical o u t p u t of t h e computing machines t o '
i n t e r p o l a t e and e x t r a p o l a t e t h e change of t h e s e i m p o r t a n t f e a t u r e s
which occur when t h e "experimental" condi t i o n s are changed.
I n seeking a s i m p l i f i e d f o r m u l a t i o n o f t h e behaviour of a

'

c l a s s of systems, w e i n e v i t a b l y t r y t o develop a c o r r e s p o n d i n g
s t a t e s treatment i n which a l l of t h e systems obey t h e same e q u a t i o n s
when each system i s c h a r a c t e r i z e d by a s e t of p a r a m e t e r s .

Thus,

t h e aerodynamical behaviour of g e o m e t r i c a l l y s i m i l a r o b j e c t s moving

through d i f f e r e n t media can be c h a r a c t e r i z e d by Reynolds, P r a n d t l ,
and Schmidt numbers.

The v o l u m e t r i c b e h a v i o n r of a gas o r l i q u i d

can be c h a r a c t e r i z e d by t h e c r i t i c a l p a r a m e t e r s :

Pc,Vc,

and Tc.

I n chemistry, a compound i s c h a r a c t e r i z e d by i t s atomic composition

and by i t s chemical bonds.

I n quantum chemistry, we f u r t h e r

c h a r a c t e r i z e a compound by i t s molecular o r b i t a l s .

Under l y i n g each

of t h e s e u s e s of corresponding s t a t e s i s t h e i n h e r e n t n o t i o n of t h e
i n t e r c h a n g e a b i l i t y of systems of a p a r t i c u l a r c l a s s .

This i n t e r -

c h a n g e a b i l i t y i s c e r t a i n l y o n l y an approximation, b u t i t may be
u s e f u l i n h e l p i n g u s t o comprehend and t o p r e d i c t t h e behaviour of
complex systems.

I n t h e p r e s e n t paper, l e t us c o n s i d e r on a simple

b a s i s , f i r s t , how S l a t e r s c r e e n i n g c o n s t a n t s r e l a t e t o t h e
i n t e r c h a n g e a b i l i t y of atomic o r b i t a l s and second, t h e i r r o l e i n
molecular o r b i t a l s .

11.

Atomic O r b i t a l s
The n o t i o n of s c r e e n i n g c o n s t a n t s stems from a well-known

theorem of c l a s s i c a l e l e c t r o s t a t i c s .

Suppose t h a t a n atom i s

composed of a n u c l e u s of c h a r g e 3. Z e

surrounded by a s p h e r i c a l l y

symmetric cloud o f e l e c t r o n s having a charge d e n s i t y

Then t h e e l e c t r o s t a t i c p o t e n t i a l

nucleus i s

V(r)

a t a distance

- eP(r).
r

from t h e

r
Here t h e s c r e e n i n g c o n s t a n t

S ( r ) = 4rrJ$r'*

of e l e c t r o n s l y i n g w i t h i n a s p h e r e of r a d i u s
c h a r ge
Zeff(r)

'eff

(r)= Z

i s t h e number

dr'

The e f f e c t i v e n u c l e a r

It i s a remarkable f a c t t h a t

S(r).

V(r)

and

a r e u n a f f e c t e d by t h a t p a r t of t h e s p h e r i c a l l y symmetric

e l e c t r o n i c c h a r g e cloud which l i e s o u t s i d e of t h e s p h e r e of r a d i u s

r.

I f t h e e l e c t r o n s were d i s t r i b u t e d i n a s e t of s p h e r i c a l s h e l l s , t h e n
f o r e l e c t r o n s i n t h e n - t h s h e l l t h e e l e c t r o s t a t i c p o t e n t i a l would be
V = e(Z-Sn)/r
Nk

where

i s the screening constant.

I f there are

e l e c t r o n s i n the k-th s h e l l , then

n-1
S

Nk

k= 1

&(Nn-l)

The r e a s o n why each of t h e o t h e r e l e c t r o n s i n t h e n - t h s h e l l i s only

h a l f e f f e c t i v e i n i t s s h i e l d i n g of a p a r t i c u l a r e l e c t r o n i s t h a t
( i f t h e s h e l l has f i n i t e t h i c k n e s s ) , i t i s e q u a l l y p r o b a b l e t h a t a n
a r b i t r a r y o t h e r e l e c t r o n has a r a d i u s g r e a t e r t h a n t h e r a d i u s of
t h e p a r t i c u l a r e l e c t r o n under c o n s i d e r a t i o n .
I n r e a l atoms, t h e atomic o r b i t a l s a r e n o t h i g h l y l o c a l i z e d
i n a spherical shell.

Thus t h e concept of a s c r e e n i n g c o n s t a n t f o r

each t y p e o f o r b i t a l r e p r e s e n t s an approximation.

And, indeed, f o r

t h e e x p e c t a t i o n v a l u e of each d i f f e r e n t t y p e of p r o p e r t y , w e should
use a d i f f e r e n t v a l u e f o r t h e s c r e e n i n g c o n s t a n t .
Already i n 1 9 2 1 Schrodinger

suggested t h a t t h e o r b i t s of t h e

s e m i - c l a s s i c a l Bohr quantum mechanics be d i v i d e d i n t o segments.

I n each of t h e s e segments, t h e e l l i p s o i d a l t r a j e c t o r i e s were

approximated by assuming a coulomb p o t e n t i a l w i t h an e f f e c t i v e
n u c l e a r charge c h a r a c t e r i s t i c of t h i s segment.

Schrodinger ' s

concept of atomic s t r u c t u r e w a s a crude b e g i n n i n g of t h e H a r t r e e

(1927,1932)
atom. I n 1927, P a u l i n g h s e d S c h r o d i n g e r ' s procedure t o e s t i m a t e
I

( r a t h e r a c c u r a t e l y ) t h e molar r e f r a c t i v i t y , t h e diamagnetic
s u s c e p t i b i l i t y , and t h e s i z e s of v a r i o u s atoms.
I n 1930, S l a t e r

made t h e use of s c r e e n i n g c o n s t a n t s simple

and p r a c t i c a l . It would have seemed l o g i c a l t o use hydrogenic

Naqvi. 1952-4, Naqvi and V i c t o r 1.964)
orbitals/
However, w i t h hydrogen-like o r b i t a l s , many of t h e
i n t e g r a l s r e q u i r e d f o r t h e e s t i m a t i o n of atomic p r o p e r t i e s a r e
quite d i f f i c u l t t o evaluate.

S l a t e r w a s impressed by Zener's

work on a n a l y t i c a l H a r t r e e wave f u n c t i o n s .

(193G)

Zener found t h a t , a s

f a r as energy i s concerned, t h e nodes i n t h e o r b i t a l s a r e q u i t e

unimportant.

Thus, S l a t e r s i m p l i f i e d t h e Zener wave f u n c t i o n s t o

obtain the familiar Slater orbitals :

n - 1

Here t h e s c r e e n i n g c o n s t a n t

exp(

(Z

S ) r / nJi

(3)

and t h e e f f e c t i v e p r i n c i p a l quantum

number are embedded parameters which S l a t e r determined s o a s t o

g i v e good v a l u e s f o r t h e x - r a y energy l e v e l s of atoms, atomic and

t h e mean v a l u e of t h e

k-th

power of t h e r a d i u s of an e l e c t r o n i s

g i v e n by t h e r e l a t i o n

Much h a s been w r i t t e n elsewhere on t h e many d i f f e r e n t t y p e s of

( H i r s c h i c l J e i , e t a 1 1464)
a p p l i c a t i o n s of S l a t e r s c r e e n i n g c o n s t a n t s / For some p r o p e r t i e s
such as the i o n i z a t i o n p o t e n t i a l s and t h e atomic r a d i i t h e y g t v e
excellent values.

For o t h e r p r o p e r t i e s , t h e y give o n l y f a i r l y

good approximations.
For r e a l l y h i g h accuracy i t i s n e c e s s a r y t o have d i f f e r e n t
screening constants for d i f f e r e n t properties.

For example, c o n s i d e r

t h e e x p e c t a t i o n v a l u e of a p r o p e r t y which v a r i e s a s

i s l a r g e , t h o s e p o r t i o n s of c o n f i g u r a t i o n s p a c e where

rk
r

If

i s large

(and t h e s c r e e n i n g by t h e o t h e r e l e c t r o n s i s l a r g e ) must be given

t h e most weight.

Thus, p r o p e r t i e s which v a r y a s

s c r e e n i n g c o n s t a n t s if k
if

i s small.

rk

require large

i s l a r g e and small s c r e e n i n g c o n s t a n t s

On t h i s account, t h e e n e r g y s c r e e n i n g c o n s t a n t

k = -1) should be less t h a n t h e diamagnetic

(corresponding t o

s u s c e p t i b i l i t y s c r e e n i n g c o n s t a n t s (corresponding t o k = 2 ) . With
(Sanders and H i r s c h f e l d e r 1 9 6 5 , and Robinson 1 9 6 5 )
t h e use of p e r t u r b a t i o n t h e o r y and h y p e r v i r i a l t h e o r e m 4
we are
now a b l e t o c a l c u l a t e good v a l u e s of t h e s c r e e n i n g c o n s t a n t s
appropriate t o a p a r t i c u l a r property.

I n the perturbation theory

c a l c u l a t i o n s , t h e s c r e e n i n g c o n s t a n t i s a d j u s t e d s o a s t o make t h e
f i r s t order c o r r e c t i o n t o the expectation value vanish.

Table 1

shows a comparison between t h e S l a t e r s c r e e n i n g c o n s t a n t v a l u e s ,

t h e p e r t u r b a t i o n t h e o r y v a l u e s ( c a l c u l a t e d w i t h hydrogenic o r b i t a l s )
and t h e e x a c t v a l u e s of t h e e x p e c t a t i o n v a l u e s f o r a number of one
electron operators

.
Table 1.

E x p e c t a t i o n Values of One E l e c t r o n O p e r a t o r s f o r
a
Helium Ground S t a t e
A l l v a l u e s a r e given i n atomic u n i t s

Opera t o r

r'
1
2
4

r1
6
r1
-2

'1

Slater Orbital
w i t h S = 0.30

Perturbation
Theory

Exact

0.882

0 . 9 2 3 (S=O. 3 7 5 )

0.929

1.038

1 . 1 7 0 (S=O. 3 9 8 )

1.192

2.694

3.745

3.944

13.05

23.63

(S=O. 4 3 4 )

(S=O. 4 6 0 )

5.78

5 . 9 7 7 (S=O. 2 7 1 )

6.017

4.913

5 . 6 1 6 (S=O. 2 2 3 )

5.688

a . Sanders and H i r s c h f e l d e r ( 1 9 6 5 ) .

8
111. Molecular O r b i t a l s
S l a t e r type o r b i t a l s (STO's) have formed t h e b u i l d i n g b l o c k s
f o r a v a s t number of c a l c u l a t i o n s on molecules (Karo and A l l e n 1960).
These have ranged from v e r y e x a c t t r e a t m e n t s on
fi e l e c t r o n c a l c u l a t i o n s .

t o semiempirical

H2

The s i m p l e r of t h e s e approaches u s e s a t

most one S l a t e r O r b i t a l on each atom of t h e molecule t o r e p r e s e n t

each molecular o r b i t a l .

The more arduous and sometimes more r e f i n e d

t r e a t m e n t s express molecular o r b i t a l s a s a l i n e a r combination of

many STO's on a l l c e n t e r s of t h e molecular system.

The

MO's o b t a i n e d

by t h e former t r e a t m e n t s may be c o n v e n i e n t l y c a l l e d minimal b a s i s

set

MO's

and by t h e l a t t e r extended b a s i s s e t

MO's.

Due t o t h e i r f e a s i b i l i t y and o f t e n t h e i r q u a l i t a t i v e s u c c e s s
minimal b a s i s s e t c a l c u l a t i o n s have been and a r e e x t e n s i v e l y pursued,
p a r t i c u l a r l y f o r l a r g e systems (more t h a n
u s e f u l now t h a t extended

STO

basis set

centers).

MO's

It is thus

very near the

Hartree-Fock s o l u t i o n s a r e a v a i l a b l e f o r many d i a t o m i c molecules

(Nesbet 1962, Kahalas and Nesbet 1963, McLean 1963, Wahl 1964, Huo 1965
Wahl e t a l , 1966a,b)
minimal

STO

basis s e t

t o p r e s e n t some comparisons between t h e

MO's

and t h e extended

STO

basis s e t

MO's.

I n Table 2 we have compared T o t a l energy, Binding Energy,

I o n i z a t i o n p o t e n t i a l s , and where r e l e v a n t d i p o l e moments.

Extensive

comparisons of t h i s s o r t which a l s o i n v o l v e quadrupole moments and

f i e l d g r a d i e n t s a r e given i n t h e p a p e r s c i t e d .
S e v e r a l p o i n t s have become c l e a r .

One i s t h a t t h e minimal b a s i s

s e t provides a poor and u n r e l i a b l e q u a n t i t a t i v e r e p r e s e n t a t i o n

9
h
h

rn

h
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d \

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4

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c o m
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m m

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10
of

the mol

ular orbital

(see, f o r example, d i p o l e moment b e h a v i o r ) ,

second t h e Hartree-Fock v a l u e s of one e l e c t r o n p r o p e r t i e s a r e q u i t e

good and d e f i n i t e w h i l e s m a l l b a s i s s e t p r o p e r t i e s can o s c i l l a t e w i d e l y
w i t h charge i n b a s i s s e t composition. Third w e o b v i o u s l y must go beyond
t h e Hartree-Fock model t o d e s c r i b e chemical b i n d i n g i n a n o n - e m p i r i c a l
(Nesbe t 1965).
manner/ Perhaps t h e most compelling r e a s o n f o r p u r s c i n g t h e e x h a u s t i v e
L

and expensive c a l c u l a t i o n s n e c e s s a r y t o o b t a i n

HF

s o l u t i o n s is t h a t

t h e y provide u s w i t h good one e l e c t r o n p r o p e r t i e s and a s o l i d and

c o n s i s t e n t p l a t f o r m from which w e can b u i l d t h e improvements n e c e s s a r y
(Das and Wahl 1966, G i l b e r t 1965)
t o a d e q u a t e l y d e s c r i b e molecules/ , Last i t i s encouraging t h a t t h e
molecular Hartree-Fock wave-function seems t o be a t t a i n a b l e w i t h a n
extended b u t manageable b a s i s s e t of

STO's, d e r i v e d from atomic SCF c a l c u l a t i o n s .

Although n o t s u f f i c i e n t a s an a c c u r a t e d k s c r i p t i o n of c h a r g e
d i s t r i b u t i o n s and n o t s u i t a b l e when c r u d e l y used f o r p r e d i c t i n g
molecular p r o p e r t i e s , t h e S l a t e r s c r e e n i n g c o n s t a n t s and t h e s i n g l e
S l a t e r atomic o r b i t a l s seem t o provide a rough measure f o r t h e s i z e
of many molecular o r b i t a l s .

Although,

of c o u r s e , t h e r e are o t h e r

molecular o r b i t a l s which a r e s o d i s t o r t e d t h a t t h e y b a r e l i t t l e
r e l a t i o n t o t h e atomic o r b i t a l s .
(Wahl, 1966)
The p r e c e d i n g p a p e r j h a s presented t h e e l e c t r o n d e n s i t y of v e r y
n e a r l y t h e Hartree-Fock molecular o r b i t a l s of t h e homonuclear d i a t o m i c
m o l e c u l e s i n t h e f i r s t row of t h e p e r i o d i c t a b l e .

As a step i n

p a r a m e t e r i z a t i o n of t h e s e o r b i t a l s , ( s i n c e w e now have them w e should

t r y t o p u t them i n a s i m p l e r form) i t i s i n t e r e s t i n g t o s e e how
a c c u r a t e l y we c a n e s t i m a t e Some g e n e r a l f e a t u r e s of t h e s e molecular
Hartree-Fock o r b i t a l s w i t h a very u n s o p h i s t i c a t e d used of S l a t e r s c r e e n i n g
constants.

F i r s t of a l l , w e c a n c o n s i d e r t h e d i s t a n c e from t h e n u c l e u s

-v

a t which a

2s

or

11

atomic o r b i t a l h a s a maximum charge d e n s i t y .

2p

According t o S l a t e r o r b i t a l s t h i s should occur a t

max

= (Z-S)

-1

I f t h e molecular o r b i t a l s were the same a s t h e atomic o r b i t a l s i n

t h e s e p a r a t e d atoms, and i f n e g l e c t of o v e r l a p i s j u s t i f i a b l e , t h e n
t h e v a l u e s of
the

2 C

'

measured towards t h e o u t s i d e of t h e molecule f o r

max

,3

2 Cu, lrcu

6g,and 1rc Hartree-Fock o r b i t a l s should

g

a l l be comparable t o t h e ( 2 - S )

-1

f o r t h e s e p a r a t e d atoms.

Table 3.

shows t h i s comparison, whereas our simple S l a t e r s c r e e n i n g c o n s t a n t

p r e d i c t i o n of t h e

max

is excellent for the

It i s v e r y poor f o r t h e 2 6

and t h e

IT

u'

36g'

and

2Su.

The n e x t q u e s t i o n which we can a s k i s how w e l l do t h e S l a t e r

s c r e e n i n g c o n s t a n t s w i t h S l a t e r o r b i t a l s p r e d i c t t h e p o s i t i o n of t h e
outermost e l e c t r o n d e n s i t y contour a s shown i n t h i p r e c e d i n g paper.
T h i s contour c o r r e s p o n d s t o a n e l e c t r o n d e n s i t y i n t h e o r b i t a l of
-5
6 . 1 x 10
eao- 3

Table 3 shows t h i s comparison.

is excellent for the

1 6 and
g

r e a l l y "look l i k e " atomic c o r e s .

The agreement

1 6 o r b i t a l s which, e x c e p t f o r
U

H2

12

Table 3
Comparison of

for Hartree-Fock Molecular O r b i t a l s w i t h

max
r
f o r S l a t e r Atomic O r b i t a l s . Here r
i s t h e d i s t nce
max
max
o u t e r foop of t h e
from t h e n u c l e u s t o t h e maximum e l e c t r o n d e n s i t y i n t h e j o r b i t a l .
The Hartree-Fock Molecular o r b i t a l s a r e g i v e n i n t h e p r e c e d i n g
paper.
Minima 1
STO
Atom

r max ( a o >
Extended B a s i s MO!s
llt

(Z-SP

Li

B2
c2

N2
O2
F2

=U

1.54

2.3

0.77

1.7

0.90

0.80

.65

1.0

.75

.65

.51

.80

.65

.50

.50

.44

.75

.60

.45

.45

.40

.38

.70

.57

.35

.35

.35

13

co

rl

bM

rn

0)

'1

r t m
fn

crl

bl

hl

I%
W
H
W

a,

Q\

m
m

In

*J.

e
l

rn

hl

b
I4

rn

In

hl

0
d

Q\

fn
rl

rl

hl
Pq

r(

CJ

hl

hl

Frc

14

For t h e o t h e r o r b i t a l s t h e o u t e r p e r i m e t e r p r e d i c t e d by non
STO's w i t h atomic s c r e e n i n g c o n s t a n t s i s q u i t e

overlapping s i n g l e
poor.

MO p e r i m e t e r shows a " p u l l i n g i n " a l o n g

The 2 b g . H a r t r e e Fock

t h e molecular a x i s r e l a t i v e t o t h e simple S l a t e r atomic o r b i t a l while

t

the

2ib,

Hartree Fock p e r i m e t e r h a s moved o u t r e l a t i v e t o t h e S l a t e r

atomic o r b i t a l .

lrc,

The

3a9 and 1~~ o r b i t a l s a l l have a much

l a r g e r p e r i m e t e r t h a n t h e corresponding S l a t e r atomic o r b i t a l .
However, t h e charge a l o n g t h i s perimeter i s e x t r e m e l y s m a l l and i t
i s o n l y as t h e y r e f l e c t more s i g n i f i c a n t s h i f t s i n c h a r g e t h a t t h e s e
o b s e r v a t i o n s a r e important.
and 4 a r i s e from

The d i f f e r e n c e s d i s p l a y e d i n T a b l e s 3

1) n e g l e c t of o v e r l a p , 2 ) t h e HF MO's form an

orthonormal s e t w h i l e t h e S l a t e r
i n a d e q u a c i e s of a s i n g l e

STO

o r m o k c u l a r , 4 ) The S l a t e r

A0

AO's a r e o n l y normalized, 3 ) The

i n r e p r e s e n t i n g any o r b i t a l , atomic
has been "frozen" i n t h e molecule

and n o t allowed t o d i s t o r t through t h e v a r i a t i o n a l procedure.

these are j u s t the

Since

consequences of t h e u s u a l assumptions made i n

t h e most simple use of s i n g l e

STO's i n molecules, t h e s e comparisons

may be i n s t r u c t i v e .
IV.
Conclusion
C e r t a i n l y t h e s e a r e c r u d e s b s e r v a t i o n s and a d e t a i l e d a n a l y s i s
7.-

of t h e s e

MO's

i s needed, b u t w e f e e l t h a t some " S l a t e r - t y p e "

p a r a m e t e r i z a t i o n of t h e s e a c c u r a t e

"MO' s "

c a n provide u s w i t h

m o l e c u l a r b u i l d i n g b l o c k s and "Molecular" S c r e e n i n g Parameters

u s e f u l f o r proceeding t o i a r g e r systems and e s t i m a t i n g moiecuiar
p r o p e r t i e s j u s t as S l a t e r Screening c o n s t a n t s have enabled u s t o
t h i n k about and r e p r e s e n t atoms a d e q u a t e l y f o r many purposes.

15

References
A l l e n , L. C. and Karo, A. M.
G i l b e r t , T. L.

Rev. Mod. Phys. 32, 275.

(1960).

J. Chem. Phys. 43, S248.

(1965).

H i r s c h f e l d e r , J. O., C u r t i s s , C . F., and B i r d , R. B. (1964).

'%Molecular Theory of Gases and Liquids" (John Wiley and Sons,
New York, 2nd P r i n t i n g ) P. 953.
Huo, W.

(1965).

J. Chem. Phys. 00,0000.

J. Chem. Phys.

Kahalas, S . L. and Nesbet, R. K. (1963).

McLean, A. D.

(1963).

J. Chem. Phys.

2,529.

2,2653.

Naqvi, A. M. (1962). "The Screened Hydrogenic Wave Functions",

Geophysical C o r p o r a t i o n of America Tech. Report 62-14-A; Naqvi,
A. M. and V i c t o r , G. A . (1964). " C a l c u l a t i o n of Wave F u n c t i o n s
and Trans i t ion Pr obab i 1i t i e s " Ge ophys i c a 1 C o r p o r a t i o n of Amer i c a
Tech. Report RTD TDR-63-3118.
Maqvi, A. M. (1964). J. Quant.
S p e c t r o s . and R a d i a t i v e T r a n s f e r (Pergamon P r e s s ) 4, 597.

36,

Nesbet, R. K.

(1962).

J. Chem. Phys.

Nesbet, R. K.

(1965).

J. Chem. Phys. 43, S30.

1518.

P a u l i n g , L. (1927). Proc. Roy. SOC. (London) A114, 181 and

P a u l i n g , L. and Sherman, J. (1932). Z e i t . f . K r i s t a l l o g r a p h i e
81, 1.

Robinson, P. D.
Sanders, W. A. and H i r s c h f e l d e r , J. 0. (1965).
2904 and (1965) 43,000.

42,

S c h r o d i n g e r , Von Erwin (1921).

S l a t e r , J. C.
Wahl, A . C .

J. Chem. Phys.

Wahl, A. C. and Das, G.

347.

Cade, P. E.,

9,
2600.

(Jan. 1966). J. Chem. Phys. 00,0000.

Wahl, A . C., S a l e s , K. D.,

J. Chem. Phys.
Wahl, A . C . ,
00,000.

4,

Phys. Rev. 36, 57.

(1930).

(1964).

Z e i t . f . Phys.

J . Chem. Phys.

Cade, P. E . ,
S a l e s , K. D.

Zener, C. (1930). Phys. Rev.

Z e i t s . f . P h y s i k 6 l , 199.

2,51;

1966a.
(1966b).

To be submitted t o

J. Chem. Phys.

Guillemin,V. and Zeger, C .

(1930).