Second order perturbation: To calculate correction in second order, we will make use

of 2 equation (11),
(H0 En(0) ) n(2) = (H 0 En(1) ) n(1) + En(2) n(0) (19)
(2) (1) (0)
and go straight for expansion of n and n in terms of unperturbed wavefunction n ,
X X
n(1) = c(1)
m m
(0)
and n(2) = c(2) (0)
m m . (20)
m m
(2) (1)
Substituting the above expression for and n
in (19), we obtain, n
X X
0
(H0 En(0) ) c(2)
m m
(0)
= (H En
(1)
) c(1) (0) (2) (0)
m m + En n
m m
X X
(0)
(Em En(0) ) c(2)
m m
(0)
= (H 0 En(1) ) c(1) (0) (2) (0)
m m + En n .
m m
(0)
As before, we take inner product with the unperturbed wavefunction k ,
 
(0)
X
(0)
(Em En(0) ) c(2)
m k , (0)
m =
m
X (0)
 X 
(0)
 
(0)

0 (0)
k , H m c(1)
m + En(1) c(1)
m k , (0)
m + En(2) k , n(0)
m m
X X X
(0) 0
or, (Em En(0) ) c(2)
m km = c(1)
m Hkm + En(1) c(1) (2)
m km + En kn
m m m
(0) (2) (1)
X
0
or, (Ek En(0) ) ck = c(1)
m Hkm + En(1) ck + En(2) kn . (21)
m
(1)
For k = n we get the second order correction to energy, keeping in mind that cn = 0,
X X H 0 H 0 X |H 0 |2
0 mn nm mn
En(2) = c(1)
m Hnm = (0) (0)
= (0) (0)
. (22)
m6=n E
m6=n n Em m6=n n Em
E
(2) (1) (1)
For k 6= n, we will get ck knowing En (13) and cm (17),
(2) (0) (1) 0
X
0
ck (Ek En(0) ) = c(1)
m Hkm + ck Hnn
m

(2) (0)
X H 0 H 0 0 H 0
Hkn
mn km nn
or, ck (Ek En(0) ) = (0) (0)
+ (0) (0)
m6=n En Em En Ek
0 H 0
Hkm 0 H 0
Hkn
(2)
X
mn nn
or, ck = (0) (0) (0) (0)
(0) (0)
. (23)
m6=n (En Em )(En Ek ) (En Ek )2
Therefore, the energy En and wavefunction n of the full Hamiltonian (1) to second order
in perturbation theory are,
X |H 0 |2
0 mn
En = En(0) + Hnn + (0) (0)
+ (24)
m6=n En Em
" #
X H 0
mn
n = n(0) + (0) (0)
m (0)

m6=n En E m

H 0 H 0 0 H 0
X X
mk kn H mn nn (0)
+
(0) (0) (0) (0)
(0) (0) 2
m + (25)
m6=n k6=n (E n E k )(En Em ) (En Em )

1
For perturbation theory to work, the corrections it produces must be small (not wildly
(0)
different from En ). But onward second order corrections in energy (24) and first order in
wavefunction (25) contain the term that must be small,
 
 0
Hmn 
  1, n 6= m
 
 (0) (0)
 En Em 

(0) (0)
otherwise it has potential to grow large if En Em , i.e. when the energy levels are
about to be degenerate. Therefore, degenerate energy levels have to be treated differently
in perturbation theory.
Examples
1. Using first order perturbation theory, calculate the energy of the n-th state for a particle
of mass m moving in an infinite potential well of length 2L with wall at x = 0 and x =
2L, which is modified at the bottom by the perturbations: (i) V0 sin(x/2L) and (ii)
V0 (x L), where  1.
2. Calculate the energy of the n-th excited state to first order perturbation for a 1-dim
infinite potential well of length 2L, with walls at x = L and x = L, which is modified at
the bottom by the following perturbations with V0  1,
 
0 V0 L x L 0 V0 L/2 x L/2
H = H =
0 elsewhere 0 elsewhere
 
0 V0 L/2 x 0 0 V0 0 x L/2
H = H =
0 elsewhere 0 elsewhere

3. For a 1-dim harmonic oscillator, the spring constant changes from k to k(1 + ), where
 is small. Calculate the first order perturbation in the energy.
4. Calculate the first order perturbation in the energy for n-th state of a 1-dim harmonic
oscillator subjected to perturbation x4 , is a constant.
5. Consider a quantum charged 1-dim harmonic oscillator, of charge q, placed in an electric
~ = E x. Find the exact expression for the energy and then use perturbation theory
field E
to calculate the same.
6. For the following set of Hamiltonians, with  1,

  1+ 0 0 0
1 0 8 0 0
(i) E0 (ii) E0
3 0 0 3 2
0 0 2 7

5 3 0 0 3 2 0 0
(iv) E0 2 3 0 0 ,
3 5 0 0
(iii) E0 0 0 8 0 0 7 2
0 0 8 0 0 2 7

(a) find the eigenvalues and eigenvectors of the unperturbed Hamiltonian, (b) diagonalize
the full Hamiltonian to find the exact eigenvalues and expand each eigenvalue to the second
power of and (c) using the first and second order perturbation theory find the approximate
energy eigenvalues and eigenstates of the full Hamiltonian.