Kirkuk University Science College

Physics Department
Lecture-4
Quantum Mechanics II
Lecturer: Dr. Salah Yagmuroglu
Stage: 3rd
Date: 05/04/2022
Time: 08:30-11:30
Approximation Methods for Stationary States ( time – independent Hamiltonian)

Approximation Methods: The application to find the energy Eigenvalues( En )and the Eigen
functions ( ψn )of a time – independent Hamiltonian that does not have exact solutions.
Most problems in quantum mechanics cannot be solved exactly, so that we resort to
approximation methods .

Approximation Methods:
1- Perturbation Theory
2- Variation Method
3- WKB Method
1. Perturbation Theory:
 It is based on the assumption that the problem we wish to solve is slightly different from a
problem that can be solved exactly.
 Small deviation is added as a correction to the energy and the wave function of exactly
solvable Hamiltonian.
 Perturbation theory builds on known exact solutions to obtain approximation solutions.
(𝟎) (𝟎) (𝟎) (𝟎)
𝑯 𝝍𝒏 = 𝑬𝒏 𝝍𝒏 ( Solved the time- independent Schrodinger equation) [ Unperturbed case]

After perturbation, the new eigen functions and eigenvalues:

𝑯 𝝍𝒏 = 𝑬𝒏 𝝍𝒏 ………………..1 ( perturbed case)
(𝟎)
𝑯 = 𝑯 + 𝝀 𝑯…………..2 Where 𝝀 ≪ 𝟏 ( small number)

By writing 𝝍𝒏 and 𝑬𝒏 as power series in λ, we get:

𝒌 (𝒌) 𝟎 (𝟎) 𝟏 (𝟏) 𝟐 (𝟐)
𝝍𝒏 = 𝒌=𝟎 𝝀 𝝍𝒏 = 𝝀𝝍𝒏 + 𝝀𝝍𝒏 + 𝝀𝝍𝒏 + ⋯ …………..3
𝒌 (𝒌) 𝟎 (𝟎) 𝟏 (𝟏) 𝟐 (𝟐)
𝑬𝒏 = 𝒌=𝟎 𝝀 𝑬𝒏 = 𝝀𝑬𝒏 + 𝝀𝑬𝒏 + 𝝀𝑬𝒏 + ⋯ ……………………4

By substituting eqs. 2, 3 and 4 into eq.1, we get:

𝟎 𝟎 𝟏 𝟐 𝟐 𝟎 𝟏 𝟐 𝟐
𝑯 + 𝝀𝑯 𝝍𝒏 + 𝝀𝝍𝒏 + 𝝀𝝍𝒏 + ⋯ = 𝑬𝒏 + 𝝀𝑬𝒏 + 𝝀𝑬𝒏 + ⋯
𝟎 𝟎 𝟎 𝟏 𝟎 𝟎 𝟐 𝟏 𝟎 𝟎 𝟎 𝟏 𝟏 𝟎
𝑯 𝝍𝒏 + 𝝀 𝑯 𝝍𝒏 + 𝑯𝝍𝒏 + 𝝀𝟐 𝑯 𝝍𝒏 + 𝑯𝝍𝒏 + ⋯ = 𝑬𝒏 𝝍𝒏 + 𝝀 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏
𝟎 𝟐 𝟏 𝟏 𝟐 𝟎
+ 𝝀𝟐 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 + ⋯
𝟏
𝑬𝒏 → 𝑭𝒊𝒓𝒔𝒕 − 𝒐𝒓𝒅𝒆𝒓 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏 𝒕𝒐 𝒕𝒉𝒆 𝒏𝒕𝒉 𝒆𝒊𝒈𝒆𝒏𝒗𝒂𝒍𝒖𝒆.
𝟐
𝑬𝒏 → 𝒔𝒆𝒄𝒐𝒏𝒅 − 𝒐𝒓𝒅𝒆𝒓 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏 𝒕𝒐 𝒕𝒉𝒆 𝒏𝒕𝒉 𝒆𝒊𝒈𝒆𝒏𝒗𝒂𝒍𝒖𝒆.
𝟏
𝝍𝒏 → 𝑭𝒊𝒓𝒔𝒕 − 𝒐𝒓𝒅𝒆𝒓 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏 𝒕𝒐 𝒕𝒉𝒆 𝒏𝒕𝒉 𝒆𝒊𝒈𝒆𝒏𝒇𝒖𝒏𝒄𝒕𝒊𝒐𝒏.
𝟐
𝝍𝒏 → 𝒔𝒆𝒄𝒐𝒏𝒅 − 𝒐𝒓𝒅𝒆𝒓 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏 𝒕𝒐 𝒕𝒉𝒆 𝒏𝒕𝒉 𝒆𝒊𝒈𝒆𝒏𝒇𝒖𝒏𝒄𝒕𝒊𝒐𝒏

By comparing left side with right side, we get:

𝟎 𝟎 𝟎 𝟏 𝟎 𝟎 𝟐 𝟏
𝟐
𝑯 𝝍𝒏 + 𝝀 𝑯 𝝍𝒏 + 𝑯𝝍𝒏 + 𝝀 𝑯 𝝍𝒏 + 𝑯𝝍𝒏 + ⋯
𝟎 𝟎 𝟎 𝟏 𝟏 𝟎 𝟎 𝟐 𝟏 𝟏 𝟐 𝟎
𝟐
= 𝑬𝒏 𝝍𝒏 + 𝝀 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 + 𝝀 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 + ⋯
𝟎 𝟎 𝟎 𝟎
𝑯 𝝍𝒏 = 𝑬𝒏 𝝍𝒏
𝟎 𝟏 𝟎 𝟎 𝟏 𝟏 𝟎
𝑯 𝝍𝒏 + 𝑯𝝍𝒏 = 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 ……………..5 [ first order (λ)]
𝟎 𝟐 𝟏 𝟎 𝟐 𝟏 𝟏 𝟐 𝟎
𝑯 𝝍𝒏 + 𝑯𝝍𝒏 = 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 ………..6 [ second order ( λ2) ]
Finding First- order correction to the energy:
𝟎 ∗ 𝟎
By taking eq.5, multiplying by 𝝍𝒏 i.e. 𝝍𝒏 , we get:

𝟎 𝟏 𝟎 𝟎 𝟏 𝟏 𝟎
𝑯 𝝍𝒏 + 𝑯𝝍𝒏 = 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 ……………..5 [ first order (λ)]
𝟎 𝟎 𝟏 𝟎 𝟎 𝟎 𝟎 𝟏 𝟏 𝟎 𝟎 𝟎
𝝍𝒏 𝑯 𝝍𝒏 + 𝝍𝒏 𝑯𝝍𝒏 = 𝑬𝒏 𝝍𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 𝝍𝒏 Where 𝑯 is Hermitian, then

𝟎 𝟎 𝟏 𝟎 𝟎 𝟏 𝟎 𝟎 𝟏
𝝍𝒏 𝑯 𝝍𝒏 = 𝑯 𝝍𝒏 𝝍𝒏 = 𝑬𝒏 𝝍𝒏 𝝍𝒏 = 𝟎

( 𝟏) ( 𝟎) ( 𝟎)
𝑬𝒏 = 𝝍𝒏 𝑯𝝍𝒏 ( First order correction to the energy which is the expectation value of the
perturbation in the unperturbed state).

( 𝟎) ( 𝟎) ( 𝟎)
𝑬𝒏 = 𝑬𝒏 + 𝝍𝒏 𝑯𝝍𝒏
 Finding First- order correction to the wave function:
From equation 5.

𝟎 𝟏 𝟎 𝟎 𝟏 𝟏 𝟎
𝑯 𝝍𝒏 + 𝑯𝝍𝒏 = 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏

Rewriting
𝟎 𝟏 𝟎 𝟏 𝟎 𝟏 𝟎
𝑯 𝝍𝒏 − 𝑬𝒏 𝝍𝒏 = −𝑯𝝍𝒏 + 𝑬𝒏 𝝍𝒏
𝟎 𝟎 𝟏 𝟏 𝟎 𝟎
𝑯 − 𝑬𝒏 𝝍𝒏 = − 𝑯 − 𝑬𝒏 𝝍𝒏 …………..7 Where 𝝍𝒏 is known function

𝟏
𝝍𝒏 can be expressed as a linear combination
𝟏 𝒏 𝟎
𝝍𝒏 = 𝒎≠𝒏 𝑪𝒎 𝝍𝒎 …………………8

By substituting eq. 8 into eq. 7, we get:

𝟎 𝟎 𝒏 𝟎 𝟏 𝟎
𝑯 − 𝑬𝒏 𝒎≠𝒏 𝑪𝒎 𝝍𝒎 = − 𝑯 − 𝑬𝒏 𝝍𝒏
𝒏 𝟎 𝟎 𝟎 𝟎 𝟏 𝟎
𝒎≠𝒏 𝑪𝒎 𝑯 𝝍𝒎 − 𝑬𝒏 𝝍𝒎 = − 𝑯 − 𝑬𝒏 𝝍𝒏
 𝒏 𝟎 𝟎 𝟎 𝟎 𝟏 𝟎
𝒎≠𝒏 𝑪𝒎 𝑯 𝝍𝒎 − 𝑬𝒏 𝝍𝒎 = − 𝑯 − 𝑬𝒏 𝝍𝒏
𝒏 𝟎 𝟎 𝟎 𝟏 𝟎 𝟎 𝟎 𝟎 𝟎
𝒎≠𝒏 𝑪𝒎 𝑬𝒎 − 𝑬𝒏 𝝍𝒎 == − 𝑯 − 𝑬𝒏 𝝍𝒏 …………9 , Where 𝑯 𝝍𝒎 = 𝑬𝒎 𝝍𝒎
𝟎 𝟎
∗
Multiplying eq.9 by (𝝍𝒎 ) → 𝝍𝒎 from left, we get:
𝟏 𝟎
𝒏 𝟎 𝟎 𝟎 𝟎 𝟎 𝟎 𝟏 𝟎 𝟎
𝒎≠𝒏 𝑪𝒎 𝑬𝒎 − 𝑬𝒏 𝝍𝒎 𝝍𝒎 = − 𝝍𝒎 𝑯 𝝍𝒏 + 𝑬𝒏 𝝍𝒎 𝝍𝒏

𝟎 𝟎
𝒏 𝝍 𝒎 𝑯 𝝍𝒏
𝑪𝒎 = 𝟎 𝟎 ………………..10
𝑬𝒏 −𝑬𝒎

Substituting eq.10 into eq. 8, we get:

(𝟎) (𝟎)
( 𝟏) (𝟎 )
𝝍𝒎 𝑯 𝝍𝒏
𝝍𝒏 = 𝒎≠𝒏 (𝟎) (𝟎) 𝝍𝒎 ( First order correction to the wave function) (non- degenerate)
𝑬𝒏 −𝑬𝒎
(𝟎) (𝟎)
( 𝟎) ( 𝟎)
𝝍𝒎 𝑯 𝝍𝒏
𝝍𝒏 = 𝝍 𝒏 + 𝒎≠𝒏 (𝟎) (𝟎) 𝝍𝒎
𝑬𝒏 −𝑬𝒎
 Lecture Five
Example:
(A) Evaluate the first - order correction to the energy of an-harmonic oscillator using the
harmonic oscillator as the unperturbed system, where the Hamiltonian of the harmonic
(𝟎) 𝑷𝟐 𝟏
oscillator is (𝑯 = + 𝒎 𝒘𝟐 𝒙𝟐 ) and the perturbation is ( 𝑯 = 𝒌𝒙𝟒 ).
𝟐𝒎 𝟐

(B) Find the first - order correction to the Eigen function of an-harmonic oscillator.
Solution(A) : We know that the energy Eigenvalues and Eigen functions of harmonic
𝜶𝟐 𝒙𝟐
(𝟎) 𝟏 (𝟎) 𝜶 − 𝟐
oscillator are ; 𝑬𝒏 = 𝒏+ ħ 𝒘, 𝝍𝒏 = 𝒆 𝑯𝒏 (𝒙)
𝟐 𝟐𝒏 𝒏! 𝝅

+∞ −𝜌2
𝑯𝒏 𝒙 𝒊𝒔 𝑯𝒆𝒓𝒎𝒊𝒕𝒆 𝒑𝒐𝒍𝒚𝒏𝒐𝒎𝒊𝒂𝒍𝒔 , −∞
𝑒 𝐻𝑛 (𝜌)𝐻𝑚 (𝜌) 𝑑𝜌 = 𝜋 2𝑛 𝑛! 𝛿𝑛𝑚

𝑯𝒏+𝟏 = 𝟐𝝆 𝑯𝒏 − 𝟐𝒏𝑯𝒏−𝟏
……………………………………………………………………………………………………………………….
𝟎 𝟎 𝟎 𝟎
𝑯 𝝍𝒏 = 𝑬𝒏 𝝍𝒏

𝟎 𝟎 ∗ ∗
𝟏 +∞ 𝟎 𝟎 +∞ 𝟎 𝟎
𝑬𝒏 = 𝝍𝒏 𝑯 𝝍𝒏 = −∞
𝝍𝒏 (𝒙) 𝑯 𝝍𝒏 𝒙 𝒅𝒙 = −∞
𝝍𝒏 𝒙 (𝒌𝒙𝟒 ) 𝝍𝒏 𝒙 𝒅𝒙
( 𝟏) ( )∗ (𝟎)
+∞ 4 𝟎 𝛼 +∞ 4 2𝑥2
𝑬𝒏 = 𝑘 −∞
𝑥 𝝍𝒏 (𝒙) 𝝍𝒏 (𝑥 )𝑑𝑥 = 𝑘 2𝑛 𝑛! 𝑥 𝑒 −𝛼 𝐻𝑛2 (𝑥 )𝑑𝑥 …………1
𝜋 −∞

𝝆 𝒅𝝆
Let 𝜶𝒙 = 𝝆 , 𝒙 = , 𝒅𝒙 = ……………2
𝜶 𝜶

Substituting eq.2 into eq.1, we get:

𝟏 𝒌 𝜶 +∞ 𝟐
𝑬𝒏 = 𝜶𝟓 𝝆𝟒 𝑯𝟐𝒏 (𝝆) 𝒆−𝝆 𝒅𝝆 …………………3
𝟐𝒏 𝒏! 𝝅 −∞

𝟏
𝑯𝒏+𝟏 = 𝟐𝝆 𝑯𝒏 − 𝟐𝒏𝑯𝒏−𝟏 → 𝑯𝒏+𝟏 + 𝟐𝒏𝑯𝒏−𝟏 = 𝟐𝝆 𝑯𝒏 → 𝝆 𝑯𝒏 = 𝟐 𝑯𝒏+𝟏 + 𝒏𝑯𝒏−𝟏
𝟏
𝝆𝟐 𝑯𝒏 = 𝟐 𝝆𝑯𝒏+𝟏 + 𝒏𝝆𝑯𝒏−𝟏
𝟏 𝟏 𝟏
𝝆𝟐 𝑯𝒏 = 𝟐 𝑯 + (𝒏 + 𝟏)𝑯𝒏 + 𝒏[𝟐 𝑯𝒏 + (𝒏 − 𝟏)𝑯𝒏−𝟐
𝟐 𝒏+𝟐

𝟐𝒏+𝟏 𝟏
𝝆𝟐 𝑯𝒏 = 𝒏 𝒏 − 𝟏 𝑯𝒏−𝟐 + 𝑯𝒏 + 𝑯
𝟐 𝟒 𝒏+𝟐

𝟐𝒏+𝟏 𝟏 𝟐
(𝝆𝟐 𝑯𝒏 )𝟐 = 𝒏 𝒏 − 𝟏 𝑯𝒏−𝟐 + 𝑯𝒏 + 𝑯 ,
𝟐 𝟒 𝒏+𝟐
+∞ −𝝆𝟐
−∞
𝒆 𝑯𝒏 (𝝆)𝑯𝒎 (𝝆) 𝒅𝝆 = 𝝅 𝟐𝒏 𝒏! 𝜹𝒏𝒎

(𝟐𝒏+𝟏)𝟐 𝟐 𝟏
𝝆𝟒 𝑯𝟐𝒏 = 𝒏𝟐 (𝒏 − 𝟏)𝟐 𝑯𝟐𝒏−𝟐 + 𝟒
𝑯𝒏 + 𝟏𝟔 𝑯𝟐𝒏+𝟐 + ⋯ …………4
Substituting eq.4 into eq.3, we get:
𝟏 𝒌 +∞ (𝟐𝒏+𝟏)𝟐 𝟏 𝟐
𝑬𝒏 = 𝟐(
𝒏 𝒏−𝟏 )𝟐 𝑯𝟐𝒏−𝟐 + 𝑯𝟐𝒏 + 𝟏𝟔 𝑯𝟐𝒏+𝟐 𝒆−𝝆 𝒅𝝆
𝜶𝟒 𝟐𝒏 𝒏! 𝝅 −∞ 𝟒
𝟏 +∞ −𝝆𝟐
𝑬𝒏 −∞
𝒆 𝑯𝒏 (𝝆)𝑯𝒎 (𝝆) 𝒅𝝆 = 𝝅 𝟐𝒏 𝒏! 𝜹𝒏𝒎

𝒌 +∞ 𝟐 −𝝆𝟐 𝒅𝝆 (𝟐𝒏+𝟏)𝟐 +∞ 𝟐 −𝝆𝟐 𝟏 +∞ 𝟐 −𝝆𝟐 𝒅𝝆

= 𝜶𝟒 𝟐𝒏 𝒏! 𝝅
𝒏𝟐 (𝒏 − 𝟏)𝟐 −∞
𝑯 𝒏−𝟐 𝒆 + 𝟒 −∞
𝑯𝒏 𝒆 𝒅𝝆 + 𝟏𝟔 −∞
𝑯 𝒏+𝟐 𝒆
𝝅 𝟐𝒏−𝟐 (𝒏−𝟐)! 𝝅 𝟐𝒏 𝒏! 𝝅 𝟐𝒏+𝟐 (𝒏+𝟐)!

𝟏 𝒌 (𝟐𝒏+𝟏)𝟐 𝟏
𝑬𝒏 = 𝒏𝟐 (𝒏 − 𝟏)𝟐 𝝅 𝟐𝒏−𝟐 (𝒏 − 𝟐)! + 𝝅 𝟐𝒏 𝒏! + 𝟏𝟔 𝝅 𝟐𝒏+𝟐 (𝒏 + 𝟐)!
𝜶𝟒 𝟐𝒏 𝒏! 𝝅 𝟒
……5
𝒏! 𝟐𝒏
𝒏! = 𝒏(𝒏 − 𝟏)(𝒏 − 𝟐)! → (𝒏 − 𝟐)! = 𝒏(𝒏−𝟏) , 𝟐𝒏−𝟐 = 𝟐𝒏 𝟐−𝟐 = , 𝟐𝒏+𝟐 = 𝟐𝒏 𝟐𝟐
𝟒
= 𝟒( 𝟐𝒏 )
(𝒏 + 𝟐)! = (𝒏 + 𝟐)(𝒏 + 𝟏)𝒏!
 ( )𝟐
𝟏 𝒌 𝟐𝒏 + 𝟏 𝟏
𝑬𝒏 = 𝟒 𝒏 𝒏𝟐 (𝒏 − 𝟏)𝟐 𝝅 𝟐𝒏−𝟐 (𝒏 − 𝟐)! + 𝝅 𝟐𝒏 𝒏! + 𝝅 𝟐𝒏+𝟐 (𝒏
𝜶 𝟐 𝒏! 𝝅 𝟒 𝟏𝟔

+ 𝟐)!
𝟏 𝒌 (𝟐𝒏+𝟏)𝟐 𝟏
𝑬𝒏 = 𝒏𝟐 (𝒏 − 𝟏)𝟐 𝟐𝒏−𝟐 (𝒏 − 𝟐)! + 𝟐𝒏 𝒏! + 𝟏𝟔 𝟐𝒏+𝟐 (𝒏 + 𝟐)!
𝜶𝟒 𝟐𝒏 𝒏! 𝟒

𝟏 𝒌 𝒏𝟐 (𝒏−𝟏)𝟐 𝟐𝒏 𝒏! (𝟐𝒏+𝟏)𝟐 𝟏 𝟒 ( 𝟐𝒏 )(𝒏+𝟐)(𝒏+𝟏)𝒏!

𝑬𝒏 = + 𝟐𝒏 𝒏! +
𝜶𝟒 𝟐𝒏 𝒏! 𝟒 𝒏(𝒏−𝟏) 𝟒 (𝟐𝒏 𝒏!) 𝟏𝟔 𝟐𝒏 𝒏!
𝟏 𝒌 𝒏(𝒏−𝟏) 𝟐𝒏+𝟏 𝟐 (𝒏+𝟐)(𝒏+𝟏)
𝑬𝒏 = + +
𝜶𝟒 𝟒 𝟒 𝟒
𝟏 𝒌
𝑬𝒏 = 𝒏𝟐 − 𝒏 + 𝟒 𝒏𝟐 + 𝟒𝒏 + 𝟏 + 𝒏𝟐 + 𝟑𝒏 + 𝟐
𝟒𝜶𝟒

𝟏 𝒌
𝑬𝒏 = 𝟒𝜶𝟒
𝟔 𝒏𝟐 + 𝟔𝒏 + 𝟑

( 𝟏)
3𝑘
𝑬𝒏 = 4
[2 𝑛 2 + 2𝑛 + 1 (𝑭𝒊𝒓𝒔𝒕 − 𝒐𝒓𝒅𝒆𝒓 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏 𝒕𝒐 𝒕𝒉𝒆 𝒆𝒏𝒓𝒈𝒚 𝒆𝒊𝒈𝒆𝒏𝒗𝒂𝒍𝒖𝒆𝒔. )
4𝛼
𝟎 𝟏
𝑬𝒏 = 𝑬𝒏 + 𝑬𝒏

𝟏 𝟑𝒌
𝑬𝒏 = 𝒏 + 𝟐 ħ𝝎 + 𝟒𝜶𝟒 𝟐 𝒏𝟐 + 𝟐𝒏 + 𝟏 (𝒆𝒏𝒓𝒈𝒚 𝒆𝒊𝒈𝒆𝒏𝒗𝒂𝒍𝒖𝒆𝒔 𝒇𝒐𝒓 𝒂𝒏 − 𝒉𝒂𝒓𝒎𝒐𝒏𝒊𝒄 𝒐𝒔𝒄𝒊𝒍𝒍𝒂𝒕𝒐𝒓 )