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

= c2A A2 d c 2B B 2 d 2c AcB ABd

=c2A c 2B 2c AcB S
 The numerator is

H d c A A c B B H c A c B d
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
BHAd
AHBd
(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