Perturbation Theory in Quantum Mechanics

Aditya Kumar Choubey

Undergraduate Student
Department of Physics - Scottish Church College

December 9, 2024

1 Time-Independent Perturbation Theory

Time-independent perturbation theory deals with systems where the Hamiltonian does not
explicitly depend on time. It is used to find corrections to the energy levels and eigenstates of
a quantum system.

1.1 Theory
Consider a Hamiltonian of the form:

H = H0 + λV, (1)

where H0 is the unperturbed Hamiltonian, V is the perturbation, and λ is a small parameter.

The unperturbed system is described by:

H0 |n(0) ⟩ = En(0) |n(0) ⟩, (2)

(0)
where En and |n(0) ⟩ are the unperturbed energy levels and eigenstates, respectively.
We seek the perturbed eigenvalues and eigenstates, assuming they can be expanded in a
power series in λ:
En = En(0) + λEn(1) + λ2 En(2) + · · · , (3)
|n⟩ = |n(0) ⟩ + λ|n(1) ⟩ + λ2 |n(2) ⟩ + · · · . (4)

1.2 First-Order Corrections

To find the first-order corrections, we start by plugging the expansions into the Schrödinger
equation:
H|n⟩ = En |n⟩. (5)
This gives us:

(H0 +λV )(|n(0) ⟩+λ|n(1) ⟩+λ2 |n(2) ⟩+· · · ) = (En(0) +λEn(1) +λ2 En(2) +· · · )(|n(0) ⟩+λ|n(1) ⟩+λ2 |n(2) ⟩+· · · ).
(6)
Equating terms of the same order in λ, we get the zeroth-order equation:

H0 |n(0) ⟩ = En(0) |n(0) ⟩, (7)

which is satisfied by the unperturbed system.

The first-order equation is:

H0 |n(1) ⟩ + V |n(0) ⟩ = En(0) |n(1) ⟩ + En(1) |n(0) ⟩. (8)

1
 Taking the inner product with ⟨n(0) | and using the orthonormality of the eigenstates, we
get:
⟨n(0) |H0 |n(1) ⟩ + ⟨n(0) |V |n(0) ⟩ = En(0) ⟨n(0) |n(1) ⟩ + En(1) ⟨n(0) |n(0) ⟩. (9)
(0)
Since ⟨n(0) |H0 |n(1) ⟩ = En ⟨n(0) |n(1) ⟩ and ⟨n(0) |n(0) ⟩ = 1, we get:

En(1) = ⟨n(0) |V |n(0) ⟩. (10)

The first-order correction to the energy is:

En(1) = ⟨n(0) |V |n(0) ⟩. (11)

To find the first-order correction to the wavefunction, we use the first-order equation:

(H0 − En(0) )|n(1) ⟩ = −(V − En(1) )|n(0) ⟩. (12)

(1)
Since En = ⟨n(0) |V |n(0) ⟩, the equation becomes:

(H0 − En(0) )|n(1) ⟩ = −(V − ⟨n(0) |V |n(0) ⟩)|n(0) ⟩. (13)

Expanding |n(1) ⟩ in terms of the unperturbed eigenstates:

X
|n(1) ⟩ = cm |m(0) ⟩, (14)
m̸=n

we get:
(0)
(Em − En(0) )cm = −⟨m(0) |V |n(0) ⟩. (15)
Therefore,
⟨m(0) |V |n(0) ⟩
cm = (0) (0)
, for m ̸= n. (16)
En − Em
So the first-order correction to the wavefunction is:
X ⟨m(0) |V |n(0) ⟩
|n(1) ⟩ = (0) (0)
|m(0) ⟩. (17)
m̸=n En − Em

1.3 Second-Order Corrections

For the second-order corrections, we need the second-order equation:

H0 |n(2) ⟩ + V |n(1) ⟩ = En(0) |n(2) ⟩ + En(1) |n(1) ⟩ + En(2) |n(0) ⟩. (18)

Taking the inner product with ⟨n(0) | and using the orthonormality of the eigenstates, we
get:
⟨n(0) |V |n(1) ⟩ = En(1) ⟨n(0) |n(1) ⟩ + En(2) ⟨n(0) |n(0) ⟩. (19)
Since ⟨n(0) |n(0) ⟩ = 1 and ⟨n(0) |n(1) ⟩ = 0 (orthogonality condition):

En(2) = ⟨n(0) |V |n(1) ⟩. (20)

Substituting |n(1) ⟩ from the first-order correction:

X |⟨m(0) |V |n(0) ⟩|2
En(2) = (0) (0)
. (21)
m̸=n En − Em

2
 The second-order correction to the energy is:
X |⟨m(0) |V |n(0) ⟩|2
En(2) = (0) (0)
. (22)
m̸=n En − Em

To find the second-order correction to the wavefunction, we use:

(H0 − En(0) )|n(2) ⟩ = −V |n(1) ⟩ + En(1) |n(1) ⟩ + En(2) |n(0) ⟩. (23)

Substituting the first-order corrections:

X ⟨m(0) |V |n(0) ⟩
(H0 − En(0) )|n(2) ⟩ = −V (0) (0)
|m(0) ⟩ + En(2) |n(0) ⟩. (24)
m̸=n En − Em

Expanding |n(2) ⟩ in terms of the unperturbed eigenstates:

X
|n(2) ⟩ = dm |m(0) ⟩, (25)
m̸=n

we get:
X ⟨m(0) |V |k (0) ⟩⟨k (0) |V |n(0) ⟩
(0)
(Em − En(0) )dm = − (0) (0)
. (26)
k̸=n En − Ek
Therefore,
X ⟨m(0) |V |k (0) ⟩⟨k (0) |V |n(0) ⟩
dm = (0) (0) (0) (0)
. (27)
k̸=n (En − Em )(En − Ek )
Thus, the second-order correction to the wavefunction is:
 
X X ⟨m(0) |V |k (0) ⟩⟨k (0) |V |n(0) ⟩
|n(2) ⟩ = 
(0) (0) (0) (0)
 |m(0) ⟩. (28)
m̸=n k̸=n (En − Em )(En − Ek )

1.4 Example: Perturbed Harmonic Oscillator

Consider a simple harmonic oscillator with a perturbation:

H = H0 + λx4 , (29)
p 2
where H0 = 2m + 21 mω 2 x2 .
The unperturbed ground state energy is:

(0) 1
E0 = ℏω. (30)
2
The first-order correction to the ground state energy is:

(1) 3ℏ2
E0 = ⟨0|λx4 |0⟩ = λ . (31)
4m2 ω 2

2 Time-Dependent Perturbation Theory

Time-dependent perturbation theory deals with systems where the Hamiltonian explicitly de-
pends on time. It is used to study the effect of a time-dependent perturbation on a quantum
system.

3
2.1 Theory
Consider a Hamiltonian of the form:

H(t) = H0 + λV (t), (32)

where H0 is the unperturbed Hamiltonian, V (t) is the time-dependent perturbation, and λ is a

small parameter.
The state of the system at time t can be expressed as:
X (0)
|ψ(t)⟩ = cn (t)e−iEn t/ℏ
|n(0) ⟩, (33)
n

(0)
where En and |n(0) ⟩ are the eigenvalues and eigenstates of the unperturbed Hamiltonian H0 .

2.2 First-Order Corrections

To find the first-order correction, we start with the time-dependent Schrödinger equation:
∂
iℏ |ψ(t)⟩ = H(t)|ψ(t)⟩. (34)
∂t
Substituting the expression for |ψ(t)⟩:
!
(0)
X dcn (t) −iEn(0) t/ℏ (0) En (0) X (0)
iℏ e |n ⟩ − i cn (t)e−iEn t/ℏ |n(0) ⟩ = (H0 + λV (t)) cn (t)e−iEn t/ℏ
|n(0) ⟩.
n
dt ℏ n
(35)
(0)
Using H0 |n(0) ⟩ = En |n(0) ⟩:
X dcn (t) (0) X (0)
iℏ e−iEn t/ℏ
|n(0) ⟩ = λ cn (t)e−iEn t/ℏ
V (t)|n(0) ⟩. (36)
n
dt n

Taking the inner product with ⟨m(0) |:

dcm (t) X (0) (0)

iℏ =λ cn (t)ei(Em −En )t/ℏ ⟨m(0) |V (t)|n(0) ⟩. (37)
dt n

(1)
To first order in λ, assume cn (t) ≈ δnm + λcn (t):
(1)
dcm (t) X (0) (0)
iℏ =λ δnm ei(Em −En )t/ℏ ⟨m(0) |V (t)|n(0) ⟩. (38)
dt n

For m ̸= n: Z t
λ (0) (0)
−En )t′ /ℏ
c(1)
m (t) = ⟨m(0) |V (t′ )|n(0) ⟩ei(Em dt′ . (39)
iℏ 0

2.3 Transition Probability

The probability of the system being in state |m(0) ⟩ at time t is:
Z t 2
λ (0) (0)
−En )t′ /ℏ
Pm←n (t) = |c(1)
m (t)|
2
= ⟨m(0) |V (t′ )|n(0) ⟩ei(Em dt′ . (40)
iℏ 0

4
2.4 Second-Order Corrections
For second-order corrections, we need to consider the second-order term in the expansion of
cn (t):
cn (t) ≈ δnm + λc(1) 2 (2)
n (t) + λ cn (t). (41)
The second-order correction term is found by solving:
(2)
dcm (t) X (0) (0)
i(Em −En )t/ℏ
iℏ =λ c(1)
n (t)e ⟨m(0) |V (t)|n(0) ⟩. (42)
dt n

(1)
Substituting cn (t):
Z Z ′
λ2 X t t (0) (0) ′ (0) (0) ′′
c(2)
m (t) = 2
⟨m(0) |V (t′ )|n(0) ⟩ei(Em −En )t /ℏ ⟨n(0) |V (t′′ )|n(0) ⟩ei(En −En )t /ℏ dt′′ dt′ .
(iℏ) n 0 0
(43)

2.5 Transition Probability to Second Order

The probability of the system being in state |m(0) ⟩ at time t to second order is:

t 2 Z Z ′
λ2 X t t
Z
λ (0) (0)
−En )t′ /ℏ
(0) (0) ′
Pm←n (t) ≈ ⟨m(0) |V (t′ )|n(0) ⟩ei(Em dt′ + 2
⟨m(0) |V (t′ )|n(0) ⟩ei(Em −En )t /ℏ ⟨n(0) |V
iℏ 0 (iℏ) n 0 0
(44)

2.6 Example: Two-Level System in an Oscillating Field

Consider a two-level system with states |1⟩ and |2⟩, and an oscillating perturbation:

V (t) = V0 cos(ωt)(σx ), (45)

where σx is the Pauli-X matrix.

The transition probability from state |1⟩ to |2⟩ is:
2
V0 sin((ω − ω21 )t/2)
P1→2 (t) = , (46)
ℏ ω − ω21
E2 −E1
where ω21 = ℏ .

References
[1] D. J. Griffiths, Introduction to Quantum Mechanics, 2nd ed., Pearson Prentice Hall, 2005.

[2] J. J. Sakurai, Modern Quantum Mechanics, Addison-Wesley, 1994.

[3] Nouredine Zettili, Quantum Mechanics: Concepts and Applications, John Wiley & Sons.