Lecture 23: Introduction to Valence Bond Theory The material in this lecture covers the following in Atkins.

14 Molecular structure Valence-bond theory 14.1 The hydrogen molecule (a) The spatial wavefunction (b) The role of the electron spin Lecture on-line Introduction to Valence Bond Theory (PowerPoint) Introduction to Valence Bond Theory (PDF) Handout for this lecture

Valence Bond Theory

Basic Theory

We shall now discuss ways to approximately solve : He (re , RN ) (re , RN ) = Ee (RN ) (re , RN )
and represent the many - electron wave - function (re , RN )

Here He = Te + VNe + Vee + VNN 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

B H

H
H

H C H H H Cl

O H

N H

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

Pair 1

Pair 2

(re , RN ) = 1(r1, r2 ) 2 (r3 , r4 ) .. i (r2i1, r2i ) j (r2 j1, r2 j ).. n (r2n1, r2n ) Pair i
Pair j
Pair n

Valence Bond Theory Basic Theory We shall now illustrate this simple theory for H2
1 rA1

H
2 rB2

We have two well separated hydrogen atoms A and B each with one electron
A
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 H2

1 rA1 A B 2 rB2

Valence Bond Theory

The hamiltonian of the H2 molecule is :

Basic Theory
1 rA1 A
rB1

r12
rA2

2 rB2 B

h2 2 e2 1 H= 1 2m 4 o rA1
h e 1 2 2 2me 4 o rB2 e2 1 e2 1 4 o rB1 4 o rA 2
e2 1 + 4 o r12
2 2

Hamiltonian of HA Hamiltonian of HB

Attraction between el. 1 and H - atom B Attraction between el. 2 and H - atom B
Re pulsion between el. 2 and el. 1 Re pulsion between A and B

e2 1 + 4 o R

Valence Bond Theory

Basic Theory
1 rA1 A rB1 rA2 R B r12 2 rB2

We can thus write the Hamiltonian as h2 2 h2 2 e2 1 H= 1 1 + +V 2m 2m 4 o R

where

e2 1 e2 1 e2 1 e2 1 e2 1 V= + 4 o rA1 4 o rA 2 4 o rA 2 4 o rB1 4 o 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
1 rA1 A rB1 rA2 R B r12 2 rB2

From the functions

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

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)

Valence Bond 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)]

Basic Theory
- Symmetric in space - anti - symmetric in spin < S2 >= 0 : singlet - Anti - symmetric in space - symmetric in spin < S2 >= 2h 2 : triplet

ms = 0
ms = 1 ms = 1

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

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

Valence Bond Theory Singlet 1 = C1[A(1)B (2) + A(1)B (2)] [ (1)(2) (1) (2)]

Basic Theory Singlet density : (1) (1) sin g (1) = HA 2 + HB 2 1+ S 1+ S 2A(1)B(1) + 1 + S2

A B A B

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)
C i insures normalization Electron density :

positive overlap density Density build up between nuclei

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

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

A(1) B(1)

dr2dr3 ..drndspin probability of finding el. Overlap between no matter where other el. 1s orbitals on A and B are

Valence Bond Theory Singlet 1 = C1[A(1)B (2) + A(1)B (2)] [ (1)(2) (1) (2)]

Basic Theory Triplet density : (1) (1) sin g (1) = HA 2 + HB 2 1 S 1 S 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) A B B A 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
J+K e2 E = 2EH + + 2 4 oR 1+ S

Triplet : JK e2 2 = C2 [A(1)B (2) A(1)B (2)] E = 2EH + + 2 [ (1)(2) + (1) (2)] 4 oR 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 :

J+K e2 E = 2EH + + 2 4 oR 1+ S Triplet : JK e2 E = 2EH + + 2 4 oR 1 S
1 rA1 A rB1

Basic Theory
r12 rA2 R B 2 rB2

2EH +

e2 4 oR

e2 1 J= A(1)A(1) dv1 r1B 4 o Int. el.1 with Nuc. B 2 e 1 dv 2 B(2)B(2) r2A 4 o

2

2EH

Int. el.2 with Nuc. A

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

singlet Triplet

e 1 B(2)B(2) A(1)A(1)dv 2dv1 r12 4 o el 1 with el 2

2EH +

e + J 4 oR 1 S 2

Valence Bond Theory Singlet : J+K e2 E = 2EH + + 2 4 oR 1+ S Triplet : JK e2 E = 2EH + + 2 4 oR 1 S

Basic Theory
A A B A B B

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

e2 1 dv 2 A(2)B(2) r2A 4 o

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)dv 2dv1 negative r12 4 o int. overlap dens with itself

Valence Bond Theory Singlet : J+K e2 E = 2EH + + 2 4 oR 1+ S

E e2 2EH + 4 oR
2EH

Basic Theory Triplet : JK e2 E = 2EH + + 2 4 oR 1 S

J K + e2 E = 2EH + 1 S 2 4 oR Triplet

e2 + J 2EH + 4 oR 1 + S 2 2EH + e + J 4 oR 1 S 2
2

singlet Triplet singlet E = 2EH +

Positive overlap density makes singlet more stable than triplet

J+K e + 1+ S2 4oR

and separate hydrogen atoms origin of chemical 2 bond

Valence Bond Theory Basic Theory It is very difficult to represent valence-bond H H 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 H

he molecular potential energy curve for the ydrogen molecule showing the variation of he energy of the molecule as the bond length s changed. The calculated curve refers to the alence-bond model.

What you should learn from this lecture 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 (r2i 1, r2i ) as (re , RN ) = 1(r1, r2 ) 2 (r3 , r4 ) ..i (r2i 1, r2i ) j (r2 j 1, r2 j ).. n (r2n 1, r2n )
You should know that the singlet function 1 = C1[A(1)B (2) + A(1)B (2)] [ (1)(2) (1) (2)] is more 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 . HA (1) HB (1) 2A(1)B(1) + + sin g (1) = 2 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

What you should learn from this lecture You are not asked to derive the expression for the density of the triplet . HA (1) HB (1) 2A(1)B(1) + trip (1) = 1 S2 1 S2 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 J+K e2 + and the triplet Esin g = 2EH + 1 + S2 4 oR
JK

e2 + Etriplet = 2EH + 1 S2 4 oR 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.