Subject CHEMISTRY

Paper No and Title 2: PHYSICAL CHEMISTRY-I

Module No 11: APPROXIMATE METHOD – PERTURBATION

THEORY
Module Tag CHE_P2_M11

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 TABLE OF CONTENTS
1. Learning Outcomes
2. Approximate methods in quantum mechanics
3. Perturbation theory
3.1 Perturbation theorem
3.2 Time independent non-degenerate perturbation
3.2.1 First order perturbation theory
3.2.1.1 First order energy correction
3.2.1.2 First order wave function correction
4. Summary

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 1. Learning Outcomes
After studying this module, you shall be able to

• Appreciate the application of perturbation theory for studying complex chemical systems
• Identify the steps involved in studying a complex system using perturbation theory
• Write Schrödinger equation for complex system using perturbation theory

2. Approximate Methods in quantum mechanics

The postulates of quantum mechanics have been successfully used for deriving exact solutions to
Schrödinger equation for problems like a particle in a one dimensional box, harmonic oscillator,
rigid rotator and hydrogen atom. However, it has been found that for any atom or molecule other
than the hydrogen atom or in other words for a multi-electron system, the Schrödinger equation
cannot be solved exactly due to the electron-electron repulsion terms.

For example: Helium atom consists of one nucleus and two electrons. The Hamiltonian for this
system is

^ h2 h2 2e 2 2e 2 e2
H =− (∇ 2
e1 + ∇ 2
e2)− ∇ 2
n − − +
8π 2 me 8π 2 mn 4πε 0 r1 4πε 0 r2 4πε 0 r12

The last term in the Hamiltonian expression is the inter-electronic repulsion term which causes
difficulty in solving the Schrödinger equation. However, approximate methods have helped to
generate solutions for such and even more complex real quantum systems. Approximate methods
have been developed for solving the Schrödinger equation to find wave function and energy of
the complex system under consideration. Two widely used approximate methods are:

• Perturbation theory
• Variation method

In this module, we shall develop the fundamental equations of perturbation theory.

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 3. Perturbation theory
In Quantum mechanics, perturbation theory is an approximate method that describes a complex
quantum system in terms of a simpler system for which the exact solution is known. Perturbation
theory has been categorized into

• Time independent perturbation theory: Proposed by Erwin Schrödinger, where the

perturbation Hamiltonian is static (i.e. it has no time dependence).

• Time dependent perturbation theory: Proposed by Paul Dirac, which studies the effect of time
dependent perturbation on a time independent Hamiltonian H0.

Over here, we shall learn about time independent perturbation theory.

3.1 Perturbation theorem

Consider a function f(x) (which is not an exact wave function like Ψo, Ψ1,………. Ψn) but satisfies
the same boundary condition as Ψo, Ψ1,………. Ψn, then function f(x) can be expressed as a linear
combination of all these functions Ψi.

n
f ( x) = ∑ a n Ψn ( x) …..(1)
0

The values of the coefficients an determine the value of the arbitrary function f(x).

To find the value of ‘an’, multiply both sides of equation (1) by Ψm* and integrate within the
boundary condition,

*
∫Ψ m ( x). f ( x)dτ = ∫ Ψm* ( x).∑ an Ψn ( x)dτ …..(2)
n

*
∫Ψ m ( x). f ( x)dτ = ∑ an ∫ Ψm* ( x).Ψn ( x)dτ …..(3)
n

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 *
Case I: If n = 0 ∫Ψ m ( x).Ψ0 ( x)dτ = 0

*
Case II: If n = 1 ∫Ψ m ( x).Ψ1 ( x)dτ = 0

*
Case III: If n = m ∫Ψ m ( x).Ψm ( x)dτ = 1

*
This means that m and n states are orthogonal and therefore, ∫Ψ m ( x).Ψn ( x)dτ = 0 for all n ≠
m.

And hence, we conclude from case III, ∑a n = ∑ ∫ Ψm* ( x). f ( x)dτ …..(4)
n

3.2 Time independent non-degenerate perturbation

We have considered a system with non-degenerate ground state, i.e., with discrete energy levels
(no degeneracy).

Consider a quantum system for which the Schrödinger equation cannot be solved,

^
HΨ=EΨ …..(5)

where ψ is the wave function of the system and E is the total energy of the system and

Hˆ = Hˆ 0 + λHˆ 1 …...(6)

where λ is the perturbation parameter and the term λĤ1 in equation (6) is the first perturbation
term.

In general, the Hamiltonian, wave function and energy for any complex system can be expressed
using Taylor series of expansion as,

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 ^ ^ ^ ^
H = H 0 + λ H 1 + λ2 H 2 + ........
Ψ = Ψ0 + λΨ1 + λ2 Ψ2 + ......... …..(7)
E = E0 + λE1 + λ2 E 2 + ..........

where Ψo is exactly solvable and the first term in each of the expressions in equation (7)
represents the unperturbed term, i.e., Ĥo, Ψo and Eo. While the remaining terms in each of the
expressions of equation (7) represents the correction terms which indicate perturbation effect.

Note: The basic assumption in perturbation theory is that the perturbation terms are smaller than
unperturbed term. If the perturbation terms are not very large, then the solution derived using
perturbation method should be close to the solution of the unperturbed system.

We will now consider the first order perturbation theory in some detail.

3.2.1 First order perturbation theory

In order to derive a solution for a complex system using the first order perturbation, the
Hamiltonian, energy and wave function for the system can be written as

^ ^ ^
H = H 0+ λ H1
Ψ = Ψ0 + λΨ1 …..(8)
E = E0 + λE1

Assuming Ĥo and Eo as exact solutions when perturbation terms are not present, the Schrödinger
equation becomes

^
H o Ψo = Eo Ψo …..(9)

Putting equation (8) in equation (5) gives,

^ ^
[ H 0 + λ H 1 ].[Ψ0 + λΨ1 ] = [ E o + λE1 ].[Ψ0 + λΨ1 ] ….(10)

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 Now rearranging the equation (10),

^ ^ ^ ^
H o Ψo + H o Ψ1λ + H 1 Ψ0 λ + λ2 H 1 Ψ1 = Eo Ψo + Eo Ψ1λ + E1Ψ0 λ + λ2 E1Ψ1 ….(11)

The first term on each side of equation (11) cancels because of equation (9). Further, the last
terms on each side can be neglected as they represent the product of two small perturbation terms.
And hence the equation (11) reduces to

^ ^
H o Ψ1λ + H 1 Ψ0 λ = Eo Ψ1λ + E1Ψ0 λ …..(12)

where Ψ1 and E1 are to be determined. The terms in equation (12) are all first order in λ while
last terms on each side in equation (11) so neglected are of second order which represent second
order corrections.

Rearranging equation (12) gives,

^ ^
( H o − E0 )Ψ1 = ( E1 − H1 ) Ψ0 ..…(13)

Equation (13) is used to calculate first order corrections to energy and wave function.

3.2.1.1 First order energy correction

Considering perturbation theorem, the first order correction to the wave function can be written as
a linear combination of the orthonormal set of functions {Ψn }

ψ 1 = ∑ an Ψn ….(14)

Substituting equation (14) in equation (13) gives,

^ ^
( H o − E0 )∑ a n Ψn = ( E1 − H 1 ) Ψ0 …..(15)

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 Multiplying both sides of equation (15) by Ψo* and integrating
^ ^
* *
∫ Ψo (H o − E0 )∑ an Ψn dτ = ∫ Ψo (E1 − H1 ) Ψ0 dτ …..(16)

Rearranging the expression (16) gives

^ ^
∑ an ∫ Ψo* (H o − Eo )Ψn dτ = ∫ Ψo* (E1 − H1 ) Ψo dτ …..(17)

Solving left hand side (L.H.S) of equation (17),

^
= ∑ an ∫ Ψo* ( H o − Eo )Ψn dτ

^
Case I: n = 0 = ao ∫ Ψo* ( H o − Eo )Ψo dτ

^
= a0 ∫ Ψo* ( H o )Ψo dτ − a0 ∫ Ψo* ( Eo )Ψo dτ

= a0 Eo ∫ Ψo* .Ψo dτ − a0 Eo ∫ Ψo* .Ψo dτ (using equation (9))

=0 …..(18)

^
= a1 Ψo* ( H o − Eo )Ψ1dτ
Case II: n =1 ∫
^
= a1 Ψo* ( H o )Ψ1dτ − a1 Ψo* ( Eo )Ψ1dτ
∫ ∫
^
= a1 Ψo* ( H o )Ψ1dτ − a1Eo *
∫ ∫ Ψ Ψ dτ
o 1

(Ĥ is an Hermitian operator and eigen functions Ψ of Hermitian operators are orthogonal)

=0 …..(19)
CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I
MODULE :11, Approximate Methods-Perturbation Theory
 Equating L. H. S. to right hand side (R.H.S) of equation (17),

^
0 = ∫ Ψo* ( E1 − H1 ) Ψ0 dτ

^
0 = ∫ Ψo* ( E1 )Ψo dτ − ∫ Ψo* ( H 1 )Ψo dτ

^
E1 = ∫ Ψo* ( H 1 )Ψo dτ …..(20)

Equation (20) is the first order correction to energy term.

Total energy of the system becomes,

^
E = Eo + ∫ Ψo* ( H 1 )Ψo dτ …..(21)

3.2.1.2 First order wavefunction correction

Using equation (15),

^ ^
( H o − E0 )∑ a n Ψn = ( E1 − H 1 ) Ψ0

Multiplying both sides of equation (15) by Ψm* and integrating

^ ^
* *
∫ Ψm (H o − E0 )∑ an Ψn dτ = ∫ Ψm (E1 − H1 ) Ψ0 dτ …..(22)

Solving L.H.S of equation (22),

^
= ∫ Ψm* ( H o − E0 )∑ an Ψn dτ

^
= ∑ an [∫ Ψm* ( H o )Ψn dτ − ∫ Ψm* (E0 )Ψn dτ

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory
 ^
Case I: n = m = ∑ am [∫ Ψm* ( H o )Ψm dτ − ∫ Ψm* (E0 )Ψm dτ

= ∑ a m [ E m − E0 ] ….(23)

^
* *
Case II: n = 0 = ∑a [ ∫ Ψ
o m ( H o )Ψodτ − ∫ Ψ (E )Ψ dτ ]
m 0 o

^
* *
∫
= ao[ Ψm ( H o )Ψodτ − Eo Ψm
∫
.Ψodτ ]

=0

^
* *
Case III: n = 1 = ∑a [ ∫ Ψ
1 m ( H o )Ψ1dτ − ∫ Ψ (E )Ψ dτ ]
m 0 1

^
* *
∫
= ao[ Ψm ( H o )Ψ1dτ − Eo Ψm
∫
.Ψ1dτ ]

=0

equating equation (23) with R.H.S of equation (22),

^
am [ Em − Eo ] = ∫ Ψm* ( E1 − H1 ) Ψ0 dτ …..(24)

^
am [ Em − Eo ] = ∫ Ψm* ( E1 )Ψo dτ − ∫ Ψm* ( H1 ) Ψ0 dτ

^
am [ Em − Eo ] = −∫ Ψm* ( H1 ) Ψ0 dτ …..(25)

Rearranging equation (25) gives,

^
*
∫Ψ m ( H 1 ) Ψ0 dτ
am = …..(26)
[ Eo − E m ]
CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I
MODULE :11, Approximate Methods-Perturbation Theory
 Putting the value of coefficient am from equation (26) into equation (14) gives,

^
*

ψ1 = ∑
∫ Ψm ( H1 ) Ψ0 dτ Ψn ……(27)
m [ Eo − E m ]

Equation (27) is first order correction to wave function.

Total wave function of the system becomes,

^
*

ψ o = Ψ0 + ∑
∫ Ψn ( H1 ) Ψ0 dτ Ψn …..(28)
m [ Eo − E m ]

5. Summary
• For a multi-electron system, the Schrödinger equation cannot be solved exactly
• Approximate methods provide route for solving the Schrödinger equation for the complex
systems
• Perturbation theory is an approximate method that solves the Schrödinger equation of the
complex system by providing successive corrections to an unperturbed problem
• The basic assumption in perturbation theory is that the perturbation terms are smaller than
unperturbed term
• Perturbation theory describes a complex quantum system in terms of a simpler unperturbed
system for which the exact solutions viz., eigen states and eigen valuesare known

ψ 1 = ∑ an Ψn
• Time independent non-degenerate first order correction
^ ^ ^

• H = H 0+ λ H1
^
E = Eo + ∫ Ψo* ( H 1 )Ψo dτ
•
^
*

ψ o = Ψ0 + ∑
∫ Ψn ( H1 ) Ψ0 dτ Ψn
• m [ Eo − E m ]

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE :11, Approximate Methods-Perturbation Theory