LECTURE 01 SOLID STATE PHYSICS -II

BORN OPPENHEIMER APPROXIMATION

The assumption that electronic motion and nuclear motion in molecules can be separated is
called Born-Oppenheimer approximation. It leads to a molecular wave function in terms of
positions of electron and nuclear positions.
WAVE FUNCTION OF A MOLECULE
The wave function “” of a molecule is the product of the electronic wave function e and
the nuclear wave function N and written as
 = e N
HAMILTONIAN OPERATOR FOR A MOLECULE
The Hamiltonian operator for a molecule has following components:
1. Operator T ˆ for kinetic energy of the nucleus.
N

2. Operator Tˆ for kinetic energy of the electrons.

e
ˆ for potential energy due to electronnuclear attraction.
3. Operator VeN
ˆ for potential energy due to electronelectron repulsion.
4. Operator V ee
ˆ for potential energy due to nuclearnuclear repulsion.
5. Operator VNN
The Hamiltonian operator for a molecule is sum of these components
^
H = T ˆ + Tˆ + V ˆ + V ˆ + V ˆ - - - - - - (1)
N e eN ee NN

 The operator T ˆ does not affect the electronic motion.

N

Hence operator Tˆ is omitted in eq(1).

N

 ˆ due to the nuclearnuclear repulsion is a constant for a fixed inter

The potential energy VNN
^
nuclear distance but changes with change in inter nuclear distance. The operator VNN does
affect the electronic energy and hence retained in eq(1).
H = Tˆ e + V ˆ + V ˆ + V ˆ
^
eN ee NN - - - - - - (2)
 The term ( Tˆ e + Vˆ +V ˆ ) is the Hamiltonian He for the electronic motion
^
eN ee
ˆ
 V is the Hamiltonian for nuclear motion.
NN
^ ^
ˆ
H = He + V NN
ILLUSTRATION
Consider a hydrogen molecule H2 consists of a nucleus “a” and nucleus “b” as shown in
fig.

 The kinetic energy operator of electrons is given as

1 1
Tˆ e =  12   22
2 2
 The potential energy operator due to electronnuclear attraction is given as
ˆ 1 1 1 1
V =    
eN ra1 rb1 ra2 rb2
 The potential energy operator due to electronelectron repulsion is given as
 2

ˆ 1
V = +
ee r12
 The potential energy operator due to nuclearnuclear repulsion is given as
1
V̂NN = + R
The Hamiltonian for hydrogen molecule is given as
H = Tˆ + V ˆ + V ˆ + V ˆ
^
e eN ee NN
^ 1 2 1 2 1 1 1 1 1 1
H =    2     + +
2 1 2 ra1 rb1 ra2 rb2 r12 R
^ ^ 1
H = He +
R
BORN OPPENHEIMER APPROXIMATION
The electrons are much lighter than nuclei. Hence the electrons in a molecule would move
much faster than nuclei. It is therefore, assumed that nuclei are fixed or stationary in a molecule
while electrons move around them. Under such conditions Schrodinger equation for a molecule
can be separated into two parts. One part is for electronic motion and second part is for nucleus
motion.
The approximation of separating the electronic motion and nuclear motion in a molecule is
called BornOppenheimer approximation. The Schrodinger equation of a molecule for moving
electrons and fixed nuclei according the BornOppenheimer approximation can be solved.
The Hamiltonian for H2molecule is
^ ^ 1
H = He +
R
The total energy of H2molecule according the BornOppenheimer approximation is given
as
1
E(R) = Ee +
R
^
Where Ee is the energy due to electronic motion. It can be calculated using Hamiltonian He
for the electronic motion and electronic wave function.