PAPER OF QUANTUM PHYSICS

THE PERTURBATION THEORY

This paper is arranged to complete the task of lecture of quantum physics

Lecturer : Drs. Supurwoko, M. Si

Arranged by
Wiyogi Waskithaningtyas Utami
K2309081

PHYSICS EDUCATION
MATHEMATICS AND SCIENCE EDUCATION DEPARTMENT
TEACHER TRAINING AND EDUCATION FACULTY
SEBELAS MARET UNIVERSITY
SURAKARTA
2012

FOREWORD
Thanks to Allah SWT who has given his blessing and of guidance to the
author so that drafting a paper titled "The Perturbation Theory" can be resolved.
Physical preparation of this paper can be solved thanks to the support and
assistance from various parties. Therefore, the authors thanks:
1. Drs. Supurwoko, M.Si as the course lecturer of Quantum Physics
2. All people who give facilitate the completion of tasks in this paper
The author realizes that this paper is far from perfect because there is no
ivory that is not cracked.. Therefore, criticisms and suggestions that are highly
desirable for the sake of building a perfect paper. However, the authors hope this
paper can be useful for the author's own and other parties in general.

Surakarta, June 2012

Author

TABLE OF CONTENTS

Foreword. ... i
Table of Contents .. ii
CHAPTER I INTRODUCTION
A. Background ...................................................................................... 1
B. Problems........................................................................................... 2
C. Purpose............................................................................................. 2

CHAPTER II CONTENTS
1. The Definition of Perturbation Theory..................................................... 3
2. Time Independent Perturbation Theory
2.1 Perturbation theory for non-degenerate system..................................4
2.2 The first order correction to the energy..............................................7
2.3 The first order correction to the wave function..................................8
2.4 The second order correction to the energy..........................................9
2.5 Perturbation theory for degenerate system.........................................10
3. Time Dependent Perturbation Theory
3.1 Time dependent potentials general formalism....................................13
3.2 Sudden Perturbation............................................................................16
3.3 Harmonic Perturbation Fermis Golden Rule.....................................16
4. Application of Perturbation Theory
4.1 Perturbation caused by uniform electric field.....................................18
4.2 Dipole moment in uniform electric field............................................19
4.3 Calculation of the static polarizability................................................20
4.4 Polarizability and electronic molecular spectroscopy........................21
4.5 Dispersion forces................................................................................22
CHAPTER III CLOSING
1. Conclusion ................................................................................................25
Bibliography..........................................................................................................26

ii

CHAPTER I
INTRODUCTION
A. Background
Quantum mechanics (QM also known as quantum physics, or quantum
theory) is a branch of physics dealing with physical phenomena where the action
is on the order of the Planck constant. Quantum mechanics departs from classical
mechanics primarily at the quantum realm of atomic and subatomic length scales.
QM provides a mathematical description of much of the dual particle-like and
wave-like behavior and interactions of energy and matter.
In advanced topics of quantum mechanics, some of these behaviors are
macroscopic and only emerge at extreme (i.e., very low or very high) energies or
temperatures. The name quantum mechanics derives from the observation that
some physical quantities can change only in discrete amounts (Latin quanta), and
not in a continuous (cf. analog) way. For example, the angular momentum of an
electron bound to an atom or molecule is quantized. In the context of quantum
mechanics, the waveparticle duality of energy and matter and the uncertainty
principle provide a unified view of the behavior of photons, electrons, and other
atomic-scale objects.
In this material we can find perturbation theory. In quantum mechanics,
perturbation theory is a set of approximation schemes directly related to
mathematical perturbation for describing a complicated quantum system in terms
of a simpler one. The idea is to start with a simple system for which a
mathematical solution is known, and add an additional "perturbing" Hamiltonian
representing a weak disturbance to the system. If the disturbance is not too large,
the various physical quantities associated with the perturbed system (e.g. its
energy levels and eigenstates) can, from considerations of continuity, be expressed
as 'corrections' to those of the simple system. These corrections, being 'small'
compared to the size of the quantities themselves, can be calculated using
approximate methods such as asymptotic series. The complicated system can
therefore be studied based on knowledge of the simpler one.

In this paper will explain about perturbation theory and what is the meaning
of perturbation theory?
B. Problems
1. What is the definition of perturbation theory?
2. What is the time independent perturbation theory?
3. What is the time dependent perturbation theory? And
4. What is the application of perturbation theory?
C. Purposes
After we arrange this paper we can know
1. The definition of perturbation theory
2. Can explain and solve about the time independent theory question
3. Can solve and explain about the time dependent theory question
4. Know the application of perturbation theory

CHAPTER II
CONTENTS
1.

The Definition of Perturbation Theory

In quantum mechanics, perturbation theory is a set of approximation

schemes directly related to mathematical perturbation for describing a

complicated quantum system in terms of a simpler one. The idea is to start with a
simple system for which a mathematical solution is known, and add an additional
"perturbing" Hamiltonian representing a weak disturbance to the system. If the
disturbance is not too large, the various physical quantities associated with the
perturbed system (e.g. its energy levels and eigenstates) can, from considerations
of continuity, be expressed as 'corrections' to those of the simple system. These
corrections, being 'small' compared to the size of the quantities themselves, can be
calculated using approximate methods such as asymptotic series. The complicated
system can therefore be studied based on knowledge of the simpler one.
As was briefly mentioned earlier, a useful way of studying theories that
cannot be solved exactly is by computing power series expansions in a small
parameter. For example, quantum electrodynamics has a small parameter, called
the fine structure constant, which is given by

2e 2
1

hc
137

Thus, if T() denotes some physical quantity of interest, one computes

T T0 T1 2 T2 ...
and the first few terms can give a very good approximation. This approach, which
is called perturbation theory, is the way superstring theories were studied until
recently. The problem is that in superstring theory there is no reason that the
expansion parameter should be small.
More significantly, there are important qualitative phenomena that are
missed in perturbation theory. The reason is that there are non-perturbative
contributions to many physically interesting quantities that have the structure
T NP exp c
Such a contribution is completely invisible in perturbation theory.

Perturbation quantum string theory can be formulated by the Feynman sumover-histories method. This amounts to associating a genus h Riemann surface,
which can be visualized as a sphere with h handles attached to it, to the h th term in
the string theory perturbation expansion. The genus h surface is identified as the
corresponding string theory Feynman diagram.
The attractive features of this approach are that there is just one diagram at
each order of the perturbation expansion and that each diagram represents an
elegant (though complicated) mathematical expression that is ultraviolet finite (no
short-distance infinities).
The main drawback of this approach is that it gives no insight into how to
go beyond perturbation theory.
2.

Time Independent Perturbation Theory

2.1 Perturbation theory for Non-degenerate System
The approach that we describe in this section is also known as Rayleigh-

Schrodinger perturbation theory. We wish to find approximate solutions of the

time-independent Schrodinger equation (TISE) for a system with Hamiltonian for
which it is difficult to find exact solutions.
^

H n En n

(1)

We assume however that we know the exact solutions (0)n of a simpler

system with Hamiltionian i.e.
^ 0

0 0

(2)

H n En n
which is not too different from

H . We further assume that the states

non degenerate or in other words E n

Ek

The small difference between

perturbation on

(0)

n are

if n k.
and

(0)

is seen as merely a

and all quantities of the system described by

(0)

H (the

perturbed system) can be expanded as a Taylor series starting from the

^

unperturbed quantities (those of

(0)

) The expansion is done in terms of a

parameter .
We have

^ ^ 0 ^ 1 ^ 2
2

H H H H . .
0

n n n 2 n .....
E n E n E n 2 E n .....
The terms n

and En

(3)

(4)
(5)

are called the first order corrections to the wave

function and energy respectively, the n

and En

are the second order

corrections and so on. The task of perturbation theory is to approximate the

energies and wave functions of the perturbed system by calculating corrections up
to a given order.
In perturbation theory we are assuming that all perturbed quantities are
functions of the parameter , i.e.

we have

(0) =

^ 0

H (), E () and

, En(0) = En

n (r; ) and that when 0

and n (r; 0) = n

r . You will remember

from your math course that the Taylor series expansion of say E n() around = 0
is
E n E n 0

dE n
d

d 2 En
d

1 d 3 En
3! d3

3 .....

(6)

By comparing this expression with (5) we see that the perturbation theory
corrections to the energy level En are related to the terms of Taylor series

expansion

by:

E n E n 0

dE n
d

d 2 En
d 2

2
0

3
1 d En
3! d3

3 ..... etc.
0

Similar relations hold for the expressions (3) and (4) for the Hamiltonian and
wave function respectively.
In many textbooks the expansion of the Hamiltonian is terminated after the

first order term, i.e.

^^ ^
0 1 as this is sufficient for many physical problems.

H H H

In some cases is a physical quantity: For example, if we have a single

electron placed in a uniform electric field along the z-axis the total perturbed

H H z ze

^^

Hamiltonian is just

where

H 0

is the Hamiltonian in the absence of the

field. The effect of the field is described by the term

ez

H 1

and the strength

of the field z plays the role of the parameter .

In other cases is just a fictitious parameter which we introduce in order to
solve a problem using the formalism of perturbation theory: For example, to
describe the two electrons of a helium atom we may construct the zeroth order
Hamiltonian

as

that

of

two

non-interacting

electrons

and

2,

^ 0

H 1 2 1 1 2 21 2 r1 2 r2 which is trivial to solve as it is the sum of two

2

single-particle Hamiltonians, one for each electron. The entire Hamiltonian for

this system however is

^ 0

H H r1 r2 which is no longer separable, so we may

^ ^ 0

use perturbation theory to find an approximate solution for

^ 0 ^ 1

H H r1 r2 H H

using the fictitious parameter as a dial which is varied continuously from 0 to

its final value 1 and takes us from the model problem to the real problem.
To calculate the perturbation corrections we substitute the series expansions
of equations (3), (4) and (5) into the TISE (1) for the perturbed system, and
rearrange and group terms according to powers of in order to get

 ^ 0 ^ ^ 0 ^ 1
0 0 0 1 0 0 1 1 0
H n En n H n H n En n En n

^ 0 ^ 1 ^ 2

2 2 1 0 0 2 1 1 2 0
H n H n H n En n En n En n

(7)

Notice how in each bracket terms of the same order are grouped (for example

^ 1

H n

1
1
is a second order term because the sum of the orders of ^ n is 2).

The powers of are linearly independent functions, so the only way that the above
equation can be satisfied for all (arbitrary) values of is if the coefficient of each
power of is zero. By setting each such term to zero we obtain the following sets
of equation

^ 0

0 0

H n En n

^ 0

(8)

^ 1

0 1 1 0
H En n En H n

8

(9)

^ 0 ^ 2 ^ 1
20 2 0 1 1
nn n n n n

H E E H E H

(10)

To simplify the expressions from now on we will use bra-ket notation,

representing

n 0 , n

wave
0

function

corrections

by

their

state

number,

so

n 1 , etc.

2.2 The First order correction to the energy

To derive an expression for calculating the first order correction to the
energy E(1), take equation (9) in ket notation

^ 0

^ 1

0 1 1 0
H En n En H n


and multiply from the left by

n 1

to obtain

(11)

^ ^ 1
0 0 1 0 1 0
n n

n H nE n nHE

(12)

^ 0

^ 1

0 1 0 0 1 1 0 0 0 0

n H n En n n En n n n H n
0

^ 1

E n n 0 n 1 E n n 0 n 1 E n n 0 H n 0
1

(13)

(14)

^ 1

0 En n 0 H n 0

(15)

where in order to go from (13) to (14) we have used the fact that the igen
functions of the unperturbed Hamiltonian

property of

^ 0

^ 0

are normalized and the Hermiticity

which allows it to operate to its eigen ket on its left

10

^ 1 ^ 0
0 0 10 0 10 0 0 1
n n

n H n H n E n En n

(16)

So, according to the result (15) the first order correction to the energy is

1 0 0

En n H n

(17)

Which is simply the expectation value of the first Hamiltonian in the state
n 0 n

of the unperturbed system.

2.3 The first order correction to the wave function

We will now derive an expression for the calculation of the first order
correction to the wave function. Multiply (9) from the left by

k 0

where k n,

to obtain

^ 0

^ 1

0 0 1 0 1 0

k H E n n k En H n

E E k n k H n
k

0 0 0 1
n

11

(18)

0 1 0

(19)

^ 1

k 0 H n
0 1

kn

0
(20)

0 0

En Ek

where in going from (18) to (19) we have made use of the orthogonal of the zero
order wave functions

En

Ek

(i.e. E n

k 0 n 0

. Also, in (20) we are allowed to divide with

because we have assumed non degeneracy of the zero order problem

0

E k 0).

To proceed in our derivation for an expression for

n 1

we will employ the

identity operator expressed in the eigen functions of the unperturbed system (zero
order eigen functions):
^

n 1 1 n 1 k 0 k 0 n 1

(21)

Before substituting (20) into the above equation we must resolve a conflict:
k must be different from n in (20) but not necessarily so in (21). This restriction
implies that the first order correction to
n

will contain no contribution from

.To impose this restriction we require that

n 0 n

for j 1. Instead of

n n 1

n 0 n 1

(this leads

. This choice of normalization

for is called intermediate normalization and of course it does not affect any
physical property calculated with

since observables are independent of the

normalization of wave functions. So now we can substitute (20) into (21) and get

12

^ 1

0 0

kHn

0 H km

n k 0 0 k 0 0
nk En Ek nk En Ek
1 0

where the matrix element H km

(22)

is defined by the above equation.

2.4 The second order correction to the energy

To derive an expression for the second order correction to the energy
multiply (10) from the left with

n 0

to obtain

^ 2 ^ 1
0 0 2 0 2 0 0 1 1
n n n
^

n H nE n E nH n E nH
^ 2 ^ 1
2 0 0 0 0

0 En n H n n H n
Where we have used the fact that

En

n 0 n 1 0

13

(23)

, we can solve equation (23) for

^ 2 ^ 1 ^ 1
2 0 0 0 1 2 0 1

En nHn nHn Hn nHn

which upon substitution of

n 1

(24)

by the expression (22) becomes

H nk 1 H kn1
0
0
k n E n E k

E n H nn 2

(25)

2.5 Perturbation Theory for Degenerate State

The perturbation theory we have developed so far applies to non-degenerate states.
For systems with degenerate states we need to modify our approach. Let us assume that
0
our zeroth order Hamiltonian has d states with energy En . We will represent these

zeroth order states as

0
n ,i

n, i

, i 1,......., d

(26)

Figure 1: Effect of a perturbation on energy levels. In this example the

perturbation removes all the degenerate of the unperturbed levels.
where now we use two indices to represent each state: the first index n runs over
the different energy eigen values while the second index i runs over the d
degenerate states for a particular energy eigenvalue. Since we have d degenerate
0
states of energy En , any linear combination of these states is also a valid state

14

 0
of energy En . However, as the perturbation parameter is varied continuously

from 0 to some finite value, it is likely that the degeneracy of the states will be
lifted (either completely or partially). The question that arises then is whether the
states n ,i

of equation (26) are the correct ones, i.e. whether they can be

continuously transformed to the (in general) non-degenerate perturbed states. It

turns out that this is usually not the case and one has to first find the correct
zero order states
d

n 0,j n, i

t 1

where the coefficients cij that mix the n ,i

ci, j

j=1,..,d

(27)

are specific to the perturbation

^ 1

and are determined by its symmetry.

0
Here we will find a way to determine the correct zeroth order states n , j

and the first order correction to the energy. To do this we start from equation 9
0
0
with n , j in place of n ,i

^ 0

^ 1

0 1 1 0
H En,in,i En,i H n,i

(28)

1
Notice that we include in the notation for the first order energy En ,i the
0

index i since the perturbation may split the degenerate energy level E n ,i . Figure 1
shows an example for a hypothetical system with six states and a three-fold
degenerate unperturbed level. Note that the perturbation splits the degenerate

15

energy level. In some cases the perturbation may have no effect on the degeneracy
or may only partly remove the degeneracy.

The next step involves multiplication from the left by n, j

^ 0

^ 1

0 0 1 0 1 0

,jn H En n,i ,jn En,iH n,i

n

(29)

^ 1

0 n, j En,i H n0,i
0 1

(30)

^ 1

0 n, j En,i H n, k cks
0 1

(31)

where we have made use of the Hermiticity of

^ 0

to set the left side to zero and

0
we have substituted the expansion (27) for n ,i . Some further manipulation of

(31) gives:

^ 1

0 1 0 0

n, j H n,k E n, j n,k c 0
0

n ,i

16

ki

(32)

 H E S c
1
jk

1
n ,i

jk

ki

(33)

We thus arrive to equation (33) which describes a system of d simultaneous

linear equations for the d unknowns cki, (k = 1, . . . , d) for the correct zero order
n 0,i . Actually, this is a homogeneous system of linear equations as all constant

coefficients (i.e. the right hand side here) are zero. The trivial solution is
obviously cki = 0 but we reject it because it has no physical meaning. As you know
from your math course, in order to obtain a non-trivial solution for such a system
we must demand that the determinant of the matrix of the coefficients is zero:
H jk1 E n 1,i S jk 0

(34)

We now observe that as E n.i occurs in every row, this determinant is actually a
dth degree polynomial in E n.i and the solution of the above equation for its d
1
roots will give us all the En ,i (i = 1, . . .d) first order corrections to the energies
1
0
of the d degenerate levels with energy E n . We can then substitute each En ,i

value into (33) to find the corresponding non-trivial solution of c ki (k = 1, . . .d)

0
coefficients, or in other words the function n ,i . Finally, you should be able to

^ 1

verify that

E1,in 0,in H n0,i , i.e. that the expression (17) we have derived which gives the

first order energy as the expectation value of the first order Hamiltonian in the
zero order wave functions still holds, provided the correct degenerate zero order
wave functions are used.
3.

Time Dependent Perturbation Theory

17

So far, we have focused largely on the quantum mechanics of systems in

which the Hamiltonian is time-independent. In such cases, the time dependence of

U e

or, when cast in terms of the eigen states of the Hamiltonian,

H n En n

t e

i H t h

0 e

i H t h

c n 0 n

i H ht

a wave packet can be developed through the time-evolution operator,

as

. Although this framework provides access to any

closed quantum mechanical system, it does not describe interaction with an

external environment such as that imposed by an external electromagnetic field. In
such cases, it is more convenient to describe the induced interactions of a small

isolated system,

H 0 , through a time-dependent interaction V (t). Examples include

the problem of magnetic resonance describing the interaction of a quantum

mechanical spin with an external time-dependent magnetic field, or the response
of an atom to an external electromagnetic field. In the following, we will develop
a formalism to treat time-dependent perturbations.
3.1 Time dependent potentials general formalism
Consider then the Hamiltonian

H H 0 V t

where all time-dependence enters

through the potential V (t). In the Schrodinger representation, the dynamics of the
system are specified by the time-dependent wave function, t
^

through the

Schrodinger equation iht t H t . However, in many cases, and in

s
s

18

particular with the current application, it is convenient to work in the Interaction

representation,1 defined by

t I e
where 0

i H0 t h

(35)
s

. With this definition, one may show that the wave

function obeys the equation of motion (exercise)

ih t t
^

VI t e Ve

0
n

(36)

i H 0 t h i H 0 t h

Where

VI t t

n c n t n

. Then, if we form the eigen function expansion,

, and contract the equation of motion with a general state,

, we obtain
ic m t V mn t e imnt c n t

(37)

where the matrix elements V t

mn

m t m

and mn E m E n h nm . To

develop some intuition for the action of a time-dependent potential, it is useful to

consider first a periodically-driven two-level system where the dynamical
equations can be solved exactly.
We now turn to consider a generic time-dependent Hamiltonian for which
an analytical solution is unavailable sadly the typical situation! In this case, we
must turn to a perturbative analysis, looking for an expansion of the basis
coefficients cn(t) in powers of the interaction,
c n t c n 0 c n 1 t c n 2 t .....
Where c n OV
m

and cn

(38)

is some (time-independent) initial state. The

program to complete this series expansion is straightforward but technical.

In the interaction representation, the state t s can be related to an initial state
t0

U I t.t 0 t 0

through

(36), we must have

the

time-evolution

operator, U I t , t 0

Since this is true for any initial state t 0

i t U I t , t 0 V1 t U I t , t 0

19

i.e

, from Eq.

with the boundary condition U I t 0 , t 0 V I t U I t , t 0 . Integrating this

equation from t0 to t formally we obtain.
t

i
dt 'V I t ' U I t ' , t 0
t0

U I t, t 0

This result provides a self-consistent equation for U I(t, t0), i.e. if we take this
expression and substitute UI(t, t0) under the integrand, we obtain
t

2 t

i
i

dt 'V I t '
t0

U I t.t 0

dt V t U t

'
'
dt V I t

t0

''

''

''

, t0

t0

Iterating this procedure, we thus obtain

U I t.t 0

n t

n 0

t n 1

dt .... dt V t V t ....V t
1

t0

t0

(39)
where the term n = 0 translates to I. Note that the operators VI(t) are organized in a
time-ordered sequence, with t0 tn tn-1 .. t1 t. With this understanding, we
can write this expression more compactly as
U I t, t 0

T e

i t
'
'
dt VI t
t0

where T denotes the time-ordering operator and its action is understood by Eq.
(39). If a system is prepared in an initial state, (i) at time t = t0, at a subsequent
time, t, the system will be in a final state,
2

cn
cn 0
t
t'

i '
i
'
'
c n t n,i dt n V1 t i 2 dt dt '' n V1 t ' m m V1 t '' i .....

t0 t0
c n 1

Recalling that

V1 eiH0 t hVeiH0 t h we thus fins that

t

'
i
c n t dt ' e init V ni t '
t0

i
c n 2 t 2

Where

dt dt
'

m t0

V nm t n V t m

''

init '

imit

''

(40)

V nm t ' V mi t ''

t0

and nm E n E m etc. In particular, the

probability of effecting a transition from state (i) to state (n) for n i is given by
Pi n c n t

c n t c n t ......
1

3.2 Sudden Perturbation

20

To further explore the time-dependent perturbation theory, we turn now to

consider the action of fast or sudden perturbations. Here we define sudden as a

perturbation in which the switch from one time-independent Hamiltonian

another

H0

H0

to

' takes place over a time much shorter than any natural period of the

system. In this case, perturbation theory is irrelevant: if the system is initially in

an eigen state

of

H0

of

H 0 , its time evolution following the switch will follow that

' , i.e. one simply has to expand the initial state as a sum over the eigen

states of

H 0 n n n ' n . The non-trivial part of the problem lies in establishing

'

n'

that the change is sudden enough. This is achieved by estimating the actual time
taken for the Hamiltonian to change, and the periods of motion associated with the
state

and with its transitions to neighboring states.

3.3 Harmonic Perturbations Fermis Golden Rule

Let us then consider a system prepared in an initial state

and perturbed

by a periodic harmonic potential V (t) = V eytt which is abruptly switched on at

time t = 0. This could represent an atom perturbed by an external oscillating
electric field, such as an incident light wave. What is the probability that, at some
later time t, the system lies in state

From Eq. (40 ), to first order in perturbation theory, we have

c f1 t

i
e i fi t 1
fVi

i fi
'

'
i fi t

dt f V i e
'

The probability of effecting the transition after a time t is therefore given by

21

Pi f c f t
1

1
2

fVi

sin fl t 2

fl

Setting , fl 2s the probability takes the form sin 2 t 2 s with

a peak at ) = 0, with maximum value t 2 and width of order 1/t giving a total
weight of order t. The function has more peaks positioned at t = n 1 2 .
These are bounded by the denominator at 1/2. For large t their contribution comes
from a range of order 1/t also, and as t - the function tends towards a function
central at the origin, but multiplied by t, i.e. the likelihood of transition is
proportional to time elapsed. We should therefore divide by t to get the transition
rate.

Finally, with the normalization,

1 sin t
replacement, lim t

sin t

2 2

t we may effect the

leading to the following

expression for the transition rate,

Ri f t lim
t

Pi f t
t

2
2

f V i fl
2

(41)

This expression is known as Fermis Golden Rule One might worry that, in
the long time limit, we found that the probability of transition is in fact diverging,
so how can we justify the use of perturbation theory? For a transition with
fl , the long time limit is reached when t 1 fl , a value that can

still be very short compared with the mean transition time, which depends on the
matrix element. In fact, Fermis Rule agrees extremely well with experiment when
applied to atomic systems.
Alternative derivation of the Golden Rule: When light falls on an atom, the
full periodic potential is not suddenly imposed on an atomic time scale, but builds
up over many cycles (of the atom and of the light). If we assume that
V t e t Ve it , with very small, V is switched on very gradually in the past,

and we are looking at times much smaller than. We can then take the initial time
to be that is,
22

c f1

i.e c f t
2

i i

i
1 e fl
fl i t ' '
f
V
i
e
dt

fVi

fl i

1
e t
2
fl 2

fVi

. Applied to the transition rate

d 1 2 s
c f t ,
dt

the identify lim 0 2 2 2 fl leads to the golden rule.

fl
From the expression for the Golden rule (40) we see that, for transitions to
occur, and to satisfy energy conservation:
a. the final states must exist over a continuous energy range to match E =

for fixed perturbation frequency , or

b. the perturbation must cover a sufficiently wide spectrum of frequency so
that a discrete transition with a fixed E is possible.
2
2
For two discrete states, since V fi Vif , we have the semi classical
result Pi f Pf a statement of detailed balance.
4.

Application of Perturbation Theory

In this section we will see how perturbation theory can be used to derive

formulas for the calculation of properties of molecules.

4.1 Perturbation caused by uniform electric field
To study a molecule inside a uniform electric field

we need to add the

following term to the Hamiltonian

^ 1

H .

(41)

which describes the interaction of the molecule with the electric field using the
dipole moment operator

which is defined as
^

qi ri

(42)

To simplify the notation in what follows we will always assume that the electric
field is applied along the z-axis in which case the dot product of (41) becomes
23

^ 1

H z . z z qi zi

(43)

You will notice that we are already using the notation of perturbation theory as we
are representing the above term as a first order Hamiltonian. The role of the
perturbation parameter is played here by the z-component of the electric field
z .

4.2 Dipole moment in uniform electric field

So far we have been using perturbation theory to find corrections to the
energy and wave functions. Here we will use perturbation theory to find
corrections to the dipole moment as a function of the electric field z , which
plays the role of the perturbation parameter . We begin by applying the
Hellmann-Feynman theorem to the energy with z as the parameter. Since

^ ^ 0 ^ 1

H H H z

, or in other words only

^ 1

depends on the parameter z , we obtain

d z z
dE
dH
dH 1

z
d z
d z
d z
d z

(44)

Let us now write the energy as a Taylor series expansion (perturbation expansion)
with respect to the z parameter at the point z = 0:
dE
E E 0
d z

dE
Where d
z

z 0

z
z 0

1 d 2 E 2
2! d z 2

z
2

z 0

1 d 3 E 3
3! d z 3

z ....
3

(45)

z 0

is the first derivative of the energy with respect to z evaluated

at z = 0, etc. Of course, the zeroth order term E(0) is the value of the energy at
z = 0. If we now differentiate the above Taylor expansion with respect to z , and
substitute for the left hand side what we found in (44), we obtain an expression for
the dipole moment in non-zero electric field

24

 dE
z
d z

d 2E

z
2
d

z 0
z

z
z 0

1 d 3 E
2 d z 3

z ....
2

(46)

z 0

We usually write the above expression as

z 0 z zz z

1
zzz z 2 ......
2

(47)

where by comparison with (46) we define following quantities as derivatives of

the energy with respect to the electric field at zero electric field ( z = 0).
The permanent dipole moment

dE 0 ^ 0
0 z 0 0
d z0

(48)

which is the first order energy correction to the ground state wavefunction.
The polarizability
d 2E

zz
2
d

(49)
z 0

and the first hyperpolarizability

d 3E

zzz
(50)
3
d z 0
4.3 Calculation of the static polarizability
We can readily derive a formula for the calculation of the polarizability from the

expression for the second order correction to the energy, E n H nm

H H
0nk kn 0 .
k n En Ek

Here we apply it to the calculation of the polarizability of the ground state

0 0 0 0

z 2E0 2
2

n0

25

0 z n n z 0
0 0

E0 En

(51)

The above is an explicit expression for the polarizability of a molecule in terms of

integrals over its wavefunctions. We can write it in the following more compact
form

z 0n z n 0
E n 0
n0

zz 2

(52)

where we have defined the dipole moment matrix elements

0 0 and

z,nm m n

the

0
0
denominator E n, 0 E n E 0 . This compact form can be used to express the

mean polarizabilty which is the property that is actually observed when a

molecule is rotating freely in the gas phase or in solution and one measures the
average of all its orientations to the applied field:
x ,0 n x n 0 y ,0 n y n 0 z ,0 n z n 0
1
2
xx yy zz
(53)
3

E n 0

3 n0

0n n0
2

3 n 0 E n 0
0n
2
3

E
n0

(54)
(55)

n0

2 1 0

^ 1 ^ 1

0 1 1 1

Hn n H H n Hn Hn to
E
E

At this point we can also use the closure approximation

eliminate the sum over states and derive a computationally much simpler but also
more approximate expression for the polarizability
2

3E

n0

0n

. n 0

3E

0n

. n 0 00 . 00

2
3E

(56)

4.4 Polarizability and electronic molecular spectroscopy

As we saw in the previous section the polarizability depends on the square
of transition dipole moments n0 between states

n 0

and

0 0

. If we now re-

write expression 55 as

2e 2
me

f n0

E
n 0

26

2
n0

(57)

where we have used the oscillator strengths f n 0 defined as

2
4me
f n0
vn0 n0
(58)
2
3e
The oscillator strengths can be determined from the intensities of the electronic
transitions of a molecule and the energies En0 from the frequencies where these
transitions occur. From expression (57) we can observe that a molecule will have
a large polarizability the higher the intensity and the lower the frequency of its
electronic transitions. We can now further approximate (57) by replacing E n0 by
its average E to obtain
2e 2
(59)
f n0
me E 2 n 0
This allows us to make use of the following standard result which is known as the
Kuhn-Thomas sum rule

f
n

n0

Ne

(60)

where Ne is the total number of electrons in the molecule. Notice that the sum rule
involves a summation over all states, including n = 0, but this is compatible with
(59) as f00 = 0 by definition. We therefore obtain
2e2 N e

(61)
me E 2
4.5 Dispersion forces
Here we will see how we can use perturbation theory to study the dispersion
force (also called London or Van der Waals force) which is the weakest form of
interaction between uncharged molecules. Dispersion forces are too weak to be
considered as chemical bonds

but they are nevertheless of great chemical

relevance as for example these are the attractive forces which keep the carbon
sheets of materials like graphite in place, cause attraction between DNA base pairs
on adjacent planes, make possible the existence of liquid phases for noble gases,
etc.
Dispersion forces are caused by the interaction between electric dipoles on
different species. These dipoles are not permanent but are brought about by
instantaneous fluctuations in the charge distribution of the species. Here we will
use perturbation theory to calculate the interaction energy due to dispersion
between two species A and B which are not charged and do not have permanent

27

dipole moments. Our zeroth order Hamiltonian is the sum of the Hamiltonians for
A and B :

^ 0 ^ 0 ^ 0 ^ 0

^ 0

0 0 0 0 0 0

H H A H B , H A n A E nA n A , H B n B E nB n B

(62)

which of course means that its zeroth order energies are the sum of the energies
for the isolated A and B species and its eigenfunctions are the products of the
eigenfunctions of the A and1 B species
^

H n A0 nB 0 E A 0 E B 0 n A0 nB 0 n A0 nB 0 n A0 nB 0 ,

(63)

This Hamiltonian completely ignores all interactions between A and B. We will

now add to it the following first order Hamiltonian

^ 1 ^ ^ ^ ^ ^ ^

1
H 3 Ax Bx Ay By2 Az Bz
40R

(64)

which (can be proved using classical electrostatics) describes the interaction

between a dipole moment on A and a dipole moment on B, the two dipoles being a
distance of R apart. Note that we have implicitly assumed here the BornOppenheimer approximation which means that we are only working with the
electronic wavefunctions and the distance R is not a variable in our wavefunctions
but it is just a parameter on which our calculations depend. Here we will study
only the ground state

28

As we have assumed that A and B have no permanent dipole moments it is easy

^ 1

0 0

to show that the first order correction to the energy 0 A E B H 0 A 0 B

is zero.

We therefore turn our attention to the second order energy as defined by equation
2

E n H nm

H H
0nk kn 0 :
k n En Ek

0 0 H
0 0
A B

A B

^ 1

0 0 H
0 0

^ 1

nA0 nB 0 0A0 0B0 H nA0 nB 0

(65)

EnA 00 A EnB 00B

n A , nB 0 A , 0 B

^ 1

0 0 0 0

^ 1

n A nB 0 A 0 B H nA0 nB 0

(66)

EnA 00 A EnB 00B

n A , nB 0 A , 0 B

0
0
where we have defined E E nA0 A E nB 0 B which is a positive quantity. We now

substitute the expression for

^ 1

which consists of 3 terms and therefore results in

9 terms. However out of the nine terms only the 3 diagonal terms are non-zero
(see Atkins for a justification) and each of the non-zero terms has the following
form:

29

^^^^
0 00 00 00 0
A xA A xA B xB B xB

0 n 0 n 0

(67)

1
0 n . 0 n . 0
9

^^^^
0 00 00 00 0
A AA AB BB B

(68)

Upon substitution of this expression into (66) we obtain the following expression

2 1
E 3
3 40 R nA,nB 0A,0B
2

^ 1

^ 1

0 0 H n n 0 0 H n n
0 0
A B

0 0 0 0
A B A B

0 0
A B

(69)

EnA00A EnB00B

from which we can deduce that the interaction is attractive (E(2) < 0) and that the
interaction energy is proportional to 1/R6.
We can do some further manipulations to obtain a more approximate yet
physically meaningful expression for E(2). To proceed we apply the closure

30

 0
0
approximation by replacing nA0 A nB 0 B with the an average value E A+EB

12 0 ^ 1 ^ 1 0 1 1 1
and apply equation H n H H n H H .
n
n n
E
E
E 2

2
1

3 4 0 R 3

2
1

3 24 0 R 6

E B

A
n A , nB 0 A , 0 B

1

E A E B

,0 AnA. A, nA ,0 A B ,0 BnB . B , nB ,0 B

A2 B2

^2

Where

A2 0A0 A 0A0 and there is no

term since we assumed that the permanent

dipole moments of A and B are zero. Having reached this stage, we can re-express
the dispersion energy by using relation (56) between the mean square dipole
moment and the polarizability (in the absence of a permanent dipole moment,
A2

3
A E A to obtain
2

3
E 2
2 2
32 0

E A E B A B

E
R6
A
B

(70)

Finally we approximate the mean excitation energy with the ionization energy of
each species E A I A to arrive at the London formula for the dispersion energy
between two non-polar species

3
E 2
2 2
32 0

I A I B A B

6
I

I
A B R

(71)

This very approximate expression can provide chemical insight from back of the
envelope calculations of the dispersion energy between atoms based on readily
available quantitites such as the polarizabilities and the ionization energies. Based

31

on this formula we expect large, highly polarisable atoms to have strong

dispersion interactions.

CHAPTER III
CLOSING
CONCLUSION
In quantum mechanics, perturbation theory is a set of approximation
schemes directly related to mathematical perturbation for describing a
complicated quantum system in terms of a simpler one. The idea is to start with a
simple system for which a mathematical solution is known, and add an additional
"perturbing" Hamiltonian representing a weak disturbance to the system. If the
disturbance is not too large, the various physical quantities associated with the
perturbed system (e.g. its energy levels and eigenstates) can, from considerations
of continuity, be expressed as 'corrections' to those of the simple system. These
corrections, being 'small' compared to the size of the quantities themselves, can be
calculated using approximate methods such as asymptotic series. The complicated
system can therefore be studied based on knowledge of the simpler one.
There are two kinds of perturbation theory, they are
a. The independent of perturbation theory
b. The dependent of perturbation theory
We also can use the perturbation theory (application of perturbation theory),
to calculate
a. Perturbation caused by uniform electric field
b. Dipole moment in uniform electric field
c. Calculation of the static polarizability
d. Polarizability and electronic molecular spectroscopy
e. Dispersion forces

BIBLIOGRAPHY

32

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33