Beruflich Dokumente
Kultur Dokumente
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
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
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
We a r e
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
F i r s t , due t o
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
.
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
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
However,
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
The'
'
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,
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 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
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 f there are
Nk
k= 1
&(Nn-l)
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
Schrodinger ' s
( 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
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
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
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
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
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
(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.
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
.
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
The
MO's o b t a i n e d
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
STO
basis s e t
MO's
and t h e extended
STO
basis s e t
MO's.
Extensive
One i s t h a t t h e minimal b a s i s
9
h
h
rn
h
h
d \
. .
m m
h
4
.
I
m
o
m
wF
. .
0;
2 s
aJ
k
m
S
-0
c o m
h m
m m
rJ
0
al
U
U
al
h
d
fl
Jz
rn
03
m
h
. .
c o d
LD
c.1
. Q.
m m
O
al
u
rn
h
rn
rl
m
m
. .
W
d
m
m
coco
aJ
2
d
d
n
- 0 .
m
m
-0
G T
. . . .
C ) m a J w
-4
rl
rl
. N.
co
m
m
. mz.
1
:
0
h
co
. . . . . . .
2 3 o "m m oo s . = 2 J
I
4
1
d
1
d
1
a
03
m
h
I
u
m
rl
h
co
rn
17
co
co
co
I
I
W
W
h
I
co
LD
m
h
m
co
0
co rn
\o
m
m h
c o d
m
m
I
. .
\o
6
0
d
."
,
m
d2J
d
I
d
I
bo
FQ
Fr
5I4
5
X
k
X
\o
_ .
m
W
m
W
al
CaJ
orn
N
I4
d
I
.rl
I4
.
10
of
the mol
ular orbital
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
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
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
2p
max
= (Z-S)
-1
2 C
'
max
,3
2 Cu, lrcu
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.
max
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.
1 6 and
g
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
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.
The 2 b g . H a r t r e e Fock
the
2ib,
atomic o r b i t a l .
lrc,
The
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
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
Since
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
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
15
References
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G i l b e r t , T. L.
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Nesbet, R. K.
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42,
J. Chem. Phys.
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9,
2600.
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