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

of λ2 equation (11),
(Ĥ0 − En(0) ) ψn(2) = −(Ĥ 0 − En(1) ) ψn(1) + En(2) ψn(0) (19)
(2) (1) (0)
and go straight for expansion of ψn and ψn in terms of unperturbed wavefunction ψn ,
X X
ψn(1) = c(1)
m ψm
(0)
and ψn(2) = c(2) (0)
m ψm . (20)
m m
(2) (1)
Substituting the above expression for and ψn
in (19), we obtain, ψn
X X
0
(Ĥ0 − En(0) ) c(2)
m ψm
(0)
= −(Ĥ − En
(1)
) c(1) (0) (2) (0)
m ψm + En ψn
m m
X X
(0)
(Em − En(0) ) c(2)
m ψm
(0)
= − (Ĥ 0 − En(1) ) c(1) (0) (2) (0)
m ψm + En ψn .
m m
(0)
As before, we take inner product with the unperturbed wavefunction ψk ,
 
(0)
X
(0)
(Em − En(0) ) c(2)
m ψk , ψ (0)
m =
m
X (0)
 X 
(0)
 
(0)

0 (0)
− ψk , Ĥ ψm c(1)
m + En(1) c(1)
m ψk , (0)
ψm + En(2) ψk , ψn(0)
m m
X X X
(0) 0
or, (Em − En(0) ) c(2)
m δkm = − c(1)
m Ĥkm + En(1) c(1) (2)
m δkm + En δkn
m m m
(0) (2) (1)
X
0
or, (Ek − En(0) ) ck =− c(1)
m Ĥkm + En(1) ck + En(2) δkn . (21)
m
(1)
For k = n we get the second order correction to energy, keeping in mind that cn = 0,
X X Ĥ 0 Ĥ 0 X |Ĥ 0 |2
0 mn nm mn
En(2) = c(1)
m Ĥnm = (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 Ĥkm + ck Ĥnn
m

(2) (0)
X Ĥ 0 Ĥ 0 0 Ĥ 0
Ĥkn
mn km nn
or, ck (Ek − En(0) ) = − (0) (0)
+ (0) (0)
m6=n En − Em En − Ek
0 Ĥ 0
Ĥkm 0 Ĥ 0
Ĥkn
(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 ψn of the full Hamiltonian (1) to second order
in perturbation theory are,
X |Ĥ 0 |2
0 mn
En = En(0) + Ĥnn + (0) (0)
+ ··· (24)
m6=n En − Em
" #
X Ĥ 0
mn
ψn = ψn(0) + (0) (0)
ψm (0)

m6=n En − E m
 
Ĥ 0 Ĥ 0 0 Ĥ 0
X X
mk kn Ĥ mn nn (0)
+ 
(0) (0) (0) (0)
− (0) (0) 2
 ψm + · · · (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
Ĥmn 
  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) λV0 sin(πx/2L) and (ii)
λV0 δ(x − L), where λ  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
Ĥ = Ĥ =
0 elsewhere 0 elsewhere
 
0 −V0 −L/2 ≤ x ≤ 0 0 V0 0 ≤ x ≤ L/2
Ĥ = Ĥ =
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 β x4 , β is a constant.
5. Consider a quantum charged 1-dim harmonic oscillator, of charge q, placed in an electric
~ = E x̂. 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 λ  1,
 
  1+λ 0 0 0
1 λ  0 8 0 0 
(i) E0 (ii) E0  
λ 3  0 0 3 −2λ 
0 0 −2λ 7
   
−5 3λ 0 0 3 2λ 0 0
 (iv) E0  2λ −3 0 √0  ,
 3λ 5 0 0   
(iii) E0  0 0 8 −λ   0 0 √ −7 2λ 
0 0 −λ −8 0 0 2λ 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 λ and (c) using the first and second order perturbation theory find the approximate
energy eigenvalues and eigenstates of the full Hamiltonian.