The variation principle

Variation principle:

If an arbitrary wavefunction is used to

calculate the energy, the value
calculated is never less than the true
energy.
The arbitrary wavefunction is called the trial
wavefunction.

d E
* H gs
 = cAA + cBB
The energy of the trial wavefunction is the
expectation value of the energy operator.

The principle implies that, if we vary the

coefficients in the trial wavefunction until the
lowest energy is achieved (by evaluating the
expectation value of the hamiltonian for each
wavefunction), then those coefficients will be
the best.

H d E d E d E

If the variation function is not normalized, it
must be multiplied by a normalization constant
N.

1 N N d N 2 d
1
N 2

* H d E
d

We must search for values of the coefficients in
the trial function that minimize the value of E.

E E
0 0
c A cB

The first step is to express the two integrals in

terms of the coefficients. The denominator is

d d cA A cB B cA A cB B d

= c 2A A2 d c 2B B 2 d 2c AcB ABd
=c 2A c 2B 2c A cB S
 The numerator is

H d c A A c B B c A c B d
H A B

c 2 BHBd
=c A2 AHAd c c AHBd
c c BHAd

B A B A B

There are some complicated integrals in this

expression, but we can combine them all into
the parameters
A AHAd
B BHBd

AHBd
BHAd
(by the hermiticity of H)

B 2c A cB
2 2
H d c A A c B

The complete expression for E is

c A A c B B 2c A cB
2 2

E
c A2 cB2 2c A cB S

E E
.......? 0 ........? 0
c A cB
 After a bit of work, we obtain

E 2 c A A c A E cB cB SE
0
c A c A cB 2c A cB
2 2

E 2 cB B cB E c A c A SE
0
cB c A cB 2c A cB
2 2

we must find values of cA and cB that satisfy the

conditions

c A A c A E cB cB SE c A A E cB SE 0
cB B cB E c A c A SE cB B E c A SE 0
A E ES c A
0
ES B E cB

A E ES
0
ES B E
Illustration Using the variation principle (1)

To find the energies E of the bonding and

antibonding orbitals of a homonuclear diatomic
molecule set with A =B = and get
A E ES
E ES 0
2 2

ES B E

The solutions of this equation are

E
1 S
Illustration 2 Using the variation principle (2)

To find the values of the coefficients cA and cB in the

linear combination that corresponds to the energy E+
from Illustration 1, we use ebove (with A =B =)
to write
c A2 B cB2 B 2c A cB
E
1 S c A2 cB2 2c A cB S