Struktur Molekul

Teori Ikatan Valensi

Valence Bond Theory

Basic Theory

We shall now discuss ways to

approximately solve :
He (re ,RN )(re ,RN ) E e (RN )(re ,RN )
and represent the many- electron
wave - function (re ,RN )

Here
e = T e V
Ne + V
ee + V NN
H

We shall start with the :

Valence Bond Theory

Basic Theory

In valence bond theory we start

by writing down the Lewis structure
of our molecule
H

H
H

Cl

(re ,RN ) 1(r1,r2 ) 2 (r3 ,r4 )

..i (r2i1,r2i ) j (r2j1,r2j ).. n (r2n1,r2n )
Pair j

Subsequently we write (re ,RN )

as the product of electron pair
functions i (r2i1,r2i ) as

Pair i

Pair n

Pair 1
Pair 2

Valence Bond Theory

Basic Theory
We shall now illustrate this simple theory for H2

We have two well separated hydrogen

atoms A and B
each with one electron

1
rA1

rB2
B

We can describe hydrogen A We can describe hydrogen B

by 1sHA (rA1)(1);1sHA (rA1)(1) by 1sHB (rB2 )(2);1sHB (rB2 )(2)
Or in short
B(2)(2);B(2)(2)
A(1)(1); A(1)(1)
We now bring the two hydrogens together to form H
2
2

rB2

rA1
A

Valence Bond Theory

Basic Theory

The ham iltonian of the

H2 molecule is :
2
e
1
2
H
1
2m
4o rA1

1
rB1

rA1

2m e

22

e
1

4o rB2

2
e2 1
e
1

4o rB1 4 r
o A2

r12

rB2

rA2

Hamiltonian of HA
Hamiltonian of HB

Attraction between el. 1 and H- atom B

Attraction between el. 2 and H- atom B

e2 1

4o r12

Repulsion between el. 2 and el. 1

e2 1

4o R

Repulsion between A and B

Valence Bond Theory

Basic Theory

We can thus write the Hamiltonian as

2

2
e
1
2
2
H
1
1
V
2m
2m
4o R

r12

rB1

rA1

rB2

rA2
A

where
e2 1
e2 1
e2 1
e2 1
e2 1
V

4o rA1 4o rA2 4o rA2 4o rB1 4o r12

Subsequently we write (re ,RN )
as the product of electron pair
functions i (r2i1,r2i ) as

(r1,r2 ,R) 1(r1,r2 )

We shall further write 1(r1,r2 ) as linear

combinations of product between
functions on A and B
A(1)(1); A(1)(1)

B(2)(2);B(2)(2)

Valence Bond Theory

Basic Theory

From the functions

A(1)(1); A(1)(1)

B(2)(2);B(2)(2)

1
rB1

rA1

We can construct Allowing for interchange of

the products:
the two affords:
A(1)(1)B(2)(2)
A(2)(2)B(1)(1)
A(1)(1)B(2)(2)
A(2)(2)B(1)(1)
A(1)(1)B(2)(2)
A(2)(2)B(1)(1)
A(1)(1)B(2)(2)
A(2)(2)B(1)(1)
We have further that
(r1,r2 ,R) 1(r1,r2 )
Must be anti symmetric
(r1,r2 ,R) 1(r1,r2 ) (r2 ,r1,R) 1(r2 ,r1 )

r12

rB2

rA2
A

Valence Bond Theory

Basic Theory

From the product functions

A(1)(1)B(2)(2) A(2)(2)B(1)(1)
A(1)(1)B(2)(2) A(2)(2)B(1)(1)
A(1)(1)B(2)(2) A(2)(2)B(1)(1)
A(1)(1)B(2)(2) A(2)(2)B(1)(1)

We can construct the

anti - symmetric linear
combinations:
1 = [A(1)B(2) A(1)B(2)]
[(1)(2) (1)(2)]
2 = [A(1)B(2) A(1)B(2)]
[(1)(2) (1)(2)]

- Symmetric in space
- anti - symmetric in spin
< S2 0 : singlet
- Anti - symmetric in space
- symmetric in spin
< S2 2

: triplet

ms 0

3 = [A(1)B(2) A(1)B(2)](1)(2)
4 = [A(1)B(2) A(1)B(2)](1)(2)

ms 1
ms 1

Valence Bond Theory

Singlet
1 = C1[A(1)B (2) A(1)B (2)]
[(1)(2) (1)(2)]

Basic Theory
Singlet density :
HA (1) HB (1)
sin g (1)

2
1 S
1 S 2
2A(1)B(1)

1 S2

triplet
2 = C2[A(1)B (2) A(1)B (2)]
[(1)(2) (1)(2)]
4 = C4 [A(1)B (2) A(1)B (2)](1)(2)
3 = C3 [A(1)B (2) A(1)B (2)](1)(2)

Ci insures normalization
Electron density :

Density build up between nuclei

(r1) * (1,2,..n)(1, 2,..n)

S 1sA (1)1sB (1)d

positive overlap density

dr2dr3 ..drn dspin

probability of finding el. Overlap between
no matter where other el.1s orbitals on A and B
are

A(1)

B(1)

Valence Bond Theory

Singlet
1 = C1[A(1)B (2) A(1)B (2)]
[(1)(2) (1)(2)]

Basic Theory
Triplet density :
HA (1) HB (1)
sin g (1)

2
1 S
1 S 2
2A(1)B(1)

1 S 2

triplet
2 = C2[A(1)B (2) A(1)B (2)]
[(1)(2) (1)(2)]
4 = C4 [A(1)B (2) A(1)B (2)](1)(2)

3 = C3 [A(1)B (2) A(1)B (2)](1)(2)

negative overlap density
Density reduced between nuclei

Valence Bond Theory

Singlet:
1 = C1[A(1)B (2) A(1)B (2)]
[(1)(2) (1)(2)]

Basic Theory

JK

e2
E 2EH

2
4oR
1 S

Triplet:
JK
e2
2 = C2[A(1)B (2) A(1)B (2)]
E 2EH

2
[(1)(2) (1)(2)]
4oR
1 S
3 = C3 [A(1)B (2) A(1)B (2)](1)(2)
4 = C4 [A(1)B (2) A(1)B (2)](1)(2)
Energy hydrogen atom

S 1sA (1)1sB (1)d

Overlap between
1s orbitals on A and B

A(1)

B(1)

Valence Bond Theory

Singlet:

Basic Theory
1

JK

e2
E 2EH

2
4oR
1 S
Triplet:
JK
e2
E 2EH

2
4oR
1 S

rB1

rA1

rB2

rA2
A

e2
1
J
A(1)A(1) dv1
4o
r1B
Int. el.1 with Nuc. B
2
e
1

B(2)B(2) dv2
4o
r2A

Int. el.2 with Nuc. A

r12

e
1
B(2)B(2) A(1)A(1)dv2dv1
4o
r12
el 1 with el 2

B
E

2EH

e2
4 oR

2EH

2
e
J
2EH
4 oR 1 S 2

2EH

e
J
4 oR 1 S 2

singlet
Triplet

Valence Bond Theory

Singlet:
JK
e2
E 2EH

2
4oR
1 S
Triplet:
JK
e2
E 2EH

2
4oR
1 S

Basic Theory
A
A

e2
1
K
A(1)B(1) dv1
4o
r1B
Int. overlap dens. with Nuc. B
e2
1

A(2)B(2) dv2
4o
r2A

B
A

K is negative for singlet

since overlap density
positive

K enters with opposite

Int. overlap dens with Nuc. A sign for triplet since
overlap density
e2
1

A(2)B(2) A(1)B(1)dv2 dv1

negative
4o
r12
int. overlap dens with itself

Valence Bond Theory

Singlet:
JK
e2
E 2EH

2
4oR
1 S
2
e
2EH
4 oR

2
K
J
e

E 2EH
2
4 oR
1 S

2EH

2
e
J
2EH
4 oR 1 S 2
2
e
J
2EH
4 oR 1 S 2

Basic Theory
Triplet:
JK
e2
E 2EH

2
4oR
1 S

Triplet

singlet
Triplet
singlet
E 2EH

Positive overlap density

makes singlet more
stable than triplet

and separate hydrogen

atoms
origin of chemical
2 bond

JK
e

1 S2 4oR

Valence Bond Theory

H

Basic Theory
It is very difficult to represent valence-bond
wavefunctions because they refer to two
electrons simultaneously. However, this
illustration is an attempt. The atomic orbital
for electron 1 is represented by the black
contours, and that of electron 2 is
represented by the green contours. The
top illustration represents A(1)B(2), and
the middle illustration represents the
contribution A(2)B(1). When the two
contributions are superimposed, there
is interference between the black
contributions and between the green
contributions, resulting in an enhanced
(two-electron) density in the internuclear
region.

Valence Bond Theory

Basic Theory
H

The molecular potential energy curve for the

hydrogen molecule showing the variation of
the energy of the molecule as the bond length
is changed. The calculated curve refers to the
valence-bond model.

Summary
You should know that :
In valence bond theory we start by writing down the
Lewis structure of our molecule Subsequently we
write (re ,RN ) as the product of electron pair functions
i (r 2i 1,r 2i ) as (re ,RN ) 1(r 1,r 2 ) 2 (r 3 ,r 4 )
..i (r 2i 1,r 2i ) j (r 2 j 1,r 2 j ).. n (r 2n 1,r 2n )
You should know that the singlet function
1 = C1[A(1)B (2) A(1)B (2)] [(1)(2) (1)(2)]
is m ore stable than the triplet (e.i.
2 =
C2 [A(1)B (2) A(1)B (2)] [(1)(2) (1)(2)]
You are not asked to derive the expression
for the density of th singlet .
(1) (1) 2A(1)B(1)
sing (1) HA 2 HB 2
1 S
1 S
1 S2
However, you should know that density
is increased in the bonding region and that
contribute to the stability of the singlet

You are not asked to derive the expression

for the density of the triplet .
HA (1) HB (1) 2A(1)B(1)
trip (1)

2
2
1 S
1 S
1 S2
However, you should know that density is decreased in
the bonding region and that contribute to the higher
energy of the triplet
You will not be required to derive the energy
expression for the singlet
JK
e2
Esing 2EH

and the triplet

2 4 R
1 S
o

e2
Etriplet 2EH

2 4 R
1 S
o
However you should know that the (negative) exchange
integral K is responsible for the lower energy of the singlet.
It is related to the buildup of charge in the bonding region.
JK