Perturbation 167

CHAPTER-10
Perturbation
Time Independent perturbation theory:
The potential energy of most of the real systems are different from the standard potentials that have been
considered till now, and an exact solution is not possible. A slight change in the potential of the system can be
treated as a perturbation. The perturbation may be time dependent or time independent. In this chapter, we
shall only discuss time independent perturbation theory.
Non-degenerate Perturbation Theory:
In this section, we consider that the perturbation is applied on a system which is not degenerate. In the time
independent perturbation approach, the Hamiltonian of the system can be written as: Hˆ  Hˆ 0  Hˆ ' ,

where Ĥ 0 is the unperturbed Hamiltonian, whose nondegenerate energy eigenvalues En0  n  0,1, 2...... 

and corresponding eigenfunctions  n0  n  0,1, 2...... are assumed to be known. The functions

 n0  n  0,1, 2...... form a complete orthonormal basis and Ĥ ' is the time independent perturbing
Hamiltonian.
 1 0 ' 0
First order correction to energy of the nth state = En   n H  n

1  m0 H '  n0
First order correction to wave function of the nth state =  n    m0
m n En0  Em0

2
 m0 H '  n0
Second order correction to energy of the nth state = En 2  
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0 0
m n En  Em

SOLVED PROBLEMS
v
1. If a perturbation of the form H   x is added in a 1-D box having length 0 to a, find the total energy of the
a
system corrected upto first order.
2 n x v
Soln. The non-perturbed states are:   sin and H '  x  Given 
a a a
a a
2 n x v 2 n x 2 v n x 2 v a2 v
 E   sin x sin dx  .  x sin 2 dx  . 
0
a a a a a a a0 a a. a 4 2
n2h2
The unperturbed energy spectrum is .
8m 2
 n2 h2 v 
Therefore, the corrected total energy upto first order    .
 8m
2
2
 168 Perturbation

1 2 1 3
2. Consider an anharmonic oscillator whose potential is kx   x . Calculate the 1st order correction to the
2 6
ground state harmonic oscillator energy.

* 1 3
Soln. As we know, E   0 6  x 0

Since, the integrand of the above integral is odd and it is integrated over a symmetric interval, it is equal to zero.
Therefore,  E  0

3. Calculate the First order correction to the ground state energy of an anharmonic oscillator whose potential
1 
energy is kx 2  x 3  bx 4
2 6
1/4 1/ 4
     3
2 /2 4      x2 / 2
Soln. The first order correction is, E     e  x  x  bx   e dx
 
  6   
1/ 4 1/ 4 1/ 4 1/ 4
    2    2     2   2
    e  x /2 x 3   e  x / 2 dx     e   x / 2 bx 4   e  x /2 dx
  6    
     
1/ 2 1/ 2
    3   x2   
4   x2
  x e dx  bx e dx
6     
 
 
1/ 2 1/ 2
   2       3   x2 
   b  x 4 e   x dx Since,    x e dx  0 
  
    6  
 1  4 1   1 3 1 3b  mk 
  2b     2b  5/2      Since,   
 4 1
 2   2 2 2 4 2   
2 2

Since, we know that E '  E0  E

1 3b
Therefore, total ground energy is  h  high order term
2
 mk  2
4 
  
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A particle of mass ‘m’ is confined in a one-dimensional box of length L. Using the first order perturbation
theory, the energy of the particle in the ground state in presence of the perturbation
  x L
 V0 1   , 0  x 
V p ( x)    L 2
 0, elsewhere

is,
 4  3 2   4  3 2  V0  4  3 2  V0
(a)  2
V
 0 (b)  2
V
 0  (c)  2  V0 (d) 
 8   8  3  8  2
Soln. The ground state function of the particle in a box is
2 x
 sin  
L  L 
Perturbation 169

 2 2
And the ground state energy E1  .
2mL2
Therefore, the first order correction of energy in the ground state
L /2
V0 2  x  x 
E0(1)   V p     1  L  sin
2
  dx
L 0  L 
L /2
V  x   2 x  
 0  1  L  1  cos    dx
L 0
L 
L /2 L /2 L /2 L /2
V0  2 x x 1 2 x 
    dx   cos dx   dx   x cos dx 
L  0 0
L 0
L L 0
L 
L /2
V  L /2 2 x  
L /2  L L /2 L /2
L 2 x 1 x2 1 2 x L
  0 x 0  sin     x  sin   21  sin 
L  2 L 0 L 2 L  2 L 0 0
L  
 0

L L /2
V 1  L2  1 L 2 x 
 0  0   cos 
L  2 2 L  4  2 2 L 0 

V0  L L L 
2 
    1  1 
L  2 8 4 
 4 2   2  4 
 V0  
 8 2 
 4  3 2 
 2  V0
 8 
Correct option is (c)

1
5. Consider a particle of mass ‘m’ subjected to a one dimensional potential V ( x)  m 2 x 2 . Then we applied
2
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a potential V p ( x)   x , where  is very less and independent of x. The first order energy correction to


ground state for positive value of x is (Given :   )
m

 2  2  2
(a) 0 (b) (c) (d)
4   2 
1/4
 1  2
2 2 
Soln. The ground state wave function of 1-D SHM is    2 
e x , where   .
   m
Therefore, first order energy correction to the ground state
1/2 
 1  2
2
E0(1)   Vp     2   x e x dx  0 (Since, the integral is odd)
   

Correct option is (a)

 170 Perturbation

b  a  x  a  x  a
6. The perturbation, H '  
0 otherwise
acts on a particle of mass ‘m’ confined in an infinite square well potential
0 a  x  a
V  x  
 otherwise
The first order correction to the ground state energy of the particle is
ba ba
(a) (b) (c) 2ba (d) ba
2 2

2 x 1 x 
Soln. The ground state wavefunction for the given potential   x   cos   cos  
2a  2a  a  2a 

b  a  x  a  x  a
The perturbation, H '  
0 otherwise
The first order correction in energy,
E '   * H dx
a a
1  x  1 x b 2 x
  cos   b a  x cos   dx =  cos    a  x  dx
a a  2a  a  2a  a a  2a 
 x  
 1  cos   a a a

b
a
a  b  x  x
   a  x  dx = 2a    a  x  dx   a cos a dx   x cos a dx  (as integral is odd)
a a 2 a a a
|| 
 0 
a
   x 
 2 a sin  
b  x   a    b  2a 2  0   ab
  ax   
2a   2   2a  
 a 
Correct option is (d)
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a
Perturbation 171

PRACTICE SET
1. For the n = 2 states of a hydrogen atom in a uniform electric field of strength F,
(a) the first-order correction to the energy equals zero for all four states.
(b) there are four different values of the energy to first order
(c) the first-order correction to the energy is proportional to F for two states.
(d) the first-order correction to the energy is proportional to F2 for two states.
2. Which one of the following statements is true for a hydrogen atom in its ground state that is placed in a uniform
z-directed electric field?
(a) The first-order correction to the energy equals zero

 
(b) the proper zeroth-order wavefunctions are 1/ 2 1s  2 pz 
(c) the second-order correction to the energy is positive
(d) the first-order correction to the wavefunction contains some 2s AO.
3. The hydrogen atom transition 3d xy  2 px is
(a) dipole allowed and z-polarized (b) dipole allowed and x-polarized
(c) dipole allowed and y-polarized (d) dipole allowed and xy-polarized
4. Which of the following integrals over all space vanish by symmetry for a hydrogen atom with nucleus at the
coordinate origin?
(1)  1s y 2 pz dv (2)  2 pz z 3d xy dv (3)  2 pz x 3d xz dv
(a) 1 only (b) 1 and 2 only (c) 1 and 3 only
(d) 2 and 3 only (e) 1, 2 and 3
5. A particle in a one-dimensional infinite potential box is perturbed as shown in figure.
(i) Find out the first order energy of the system.
(ii) Calculate the second order correction for the lowest eigenvalue

0
V=0.1E1
O L/2 L
1
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An electron moving in a simple harmonic potential V 
2
2
kx is subjected to a perturbation Hˆ '  Ex where E

is the strength of the electric field which is applied in the x-direction. Determine the effect of first and second
order perturbation on the energy.
7. A hydrogen atom is exposed to an electric field of strength F applied in the z-direction. Calculate the first order
and the second order effects for the ground state of the atom (Stark effect).
ANSWER KEY

1. (c) 2. (a) 3. (c) 4. (b)

2
1.05 h 2 4  h 
5. (i) , (ii) 6.196  10   6. (zero)
 8m 
2
8m 2

1 0 1 2  218  2
7.   2
i E  0,   2
ii E   au ,   1  11  F
iii E  
8 3 