Perturbation Theory 2

Perturbation Theory
Ana Claudia Monteiro Carvalho

Natural Science Department
1
Nondegenerate Perturbation Theory
First and Second Order Corrections
Examples: Harmonic Oscillator, Potential

Wall, Hydrogen atom, Helium atom
Outline
Perturbation Theory for a degenerate

energy level
2
Quantum Physics/Chemistry
Second major quantum-mechanical

approximation method.
We will study time-independente

Objectives
Schrödinger equations for systems

under influence of some force.
3
Suppose we have a system with a time-independent Hamiltonian
෡ and we are unable to solve the Schrödinger equation
𝐻
෡ 𝑛 = 𝐸𝑛 𝜓𝑛
𝐻𝜓
Suppose also that the Hamiltonian 𝐻෡ is only slightly different from

෡ 0 of a system whose Schrödinger equation
the Hamiltonian 𝐻
෡ 0 𝜓𝑛0 = 𝐸𝑛0 𝜓𝑛0

𝐻
We are able to solve. An example is the one-dimensional

unharmonic oscillator with ℏ2 𝑑 2 1
෡=−
𝐻 + 𝑘𝑥 2
2𝑚 𝑑𝑥 2 2
ℏ2 𝑑 2 1 2
෡
𝐻=− + 𝑘𝑥 + 𝑐𝑥 3 + 𝑑𝑥 4
2𝑚 𝑑𝑥 2 2
෡′ ≡ 𝐻
𝐻 ෡−𝐻
෡0
Perturbed system
Unperturbed system
෡ ′ = 𝑐𝑥 3 + 𝑑𝑥 4
𝐻
We shall imagine that the perturbation is applied gradually, giving

a continuous change form the unperturbed to the perturbed
system. Mathematically, this corresponds to introducing a
parameter λ into the Hamiltonian, so that
෡=𝐻
𝐻 ෡ 0 +𝜆𝐻
෡′
𝜆=1
perturbation is fully turned on
First and Second Order Corrections ෡ 𝑛= 𝐻
𝐻𝜓 ෡ 0 +𝜆𝐻
෡ ′ 𝜓𝑛 = 𝐸𝑛 𝜓𝑛
perturbed wave function
𝜓𝑛 = 𝜓𝑛 𝜆, 𝑞 𝑎𝑛𝑑 𝐸𝑛 = 𝐸𝑛 𝜆
We now expand 𝜓𝑛 and 𝐸𝑛 as Taylor series in powers of 𝜆
𝜕𝜓𝑛 𝜕 2 𝜓𝑛 𝜆2
𝜓𝑛 = 𝜓𝑛 ቚ + ቤ 𝜆+ 2
อ +⋯
𝜆=0 𝜕𝜆 𝜆=0 𝜕𝜆 2!
𝜆=0
0
𝜆 → 0 ⇒ 𝜓𝑛 = 𝜓𝑛
𝜕𝐸𝑛 𝜕 2 𝐸𝑛 𝜆2
𝐸𝑛 = 𝐸𝑛 ቚ + ቤ 𝜆+ 2
อ +⋯
𝜆=0 𝜕𝜆 𝜆=0 𝜕𝜆 2!
𝜆=0
0
𝜆→0 ⇒ 𝐸𝑛 = 𝐸𝑛
Nondegenerate Perturbation Theory 0 1 2 𝑘
𝜓𝑛 = 𝜓𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯ + 𝜆𝑘 𝜓𝑛 + ⋯
0 1 2 𝑘
𝐸𝑛 = 𝐸𝑛 + 𝜆𝐸𝑛 + 𝜆2 𝐸𝑛 + ⋯ + 𝜆𝑘 𝐸𝑛 + ⋯
Considering the normalization condition for unperturbed

eigenfunction:
0 0
𝜓𝑛 𝜓𝑛 =1
0 0 0 1 0 2
1 = 𝜓𝑛 𝜓𝑛 + 𝜆 𝜓𝑛 𝜓𝑛 + 𝜆2 𝜓𝑛 𝜓𝑛 +⋯
(0) (0)
Equating the 𝜆0 coefficient, we have 1 = 𝜓𝑛 𝜓𝑛 , which is
0
satisfied since 𝜓𝑛 is normalized. Equating the coefficients 𝜆1 , 𝜆2 ,
and so on, we have:
0 1 0 2
𝜓𝑛 𝜓𝑛 =0 𝜓𝑛 𝜓𝑛 =0
෡ 0 +𝜆𝐻
෡′ 0 1 2
𝐻 𝜓𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯
0 1 2 0 1 2
= 𝐸𝑛 + 𝜆𝐸𝑛 + 𝜆2 𝐸𝑛 + ⋯ 𝜓𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯
෡ 0 𝜓𝑛0 + 𝜆 𝐻
𝐻 ෡ ′ 𝜓𝑛0 + 𝐻
෡ 0 𝜓𝑛1 ෡ 0 𝜓𝑛2 + 𝐻
+ 𝜆2 𝐻 ෡ ′ 𝜓𝑛1 +⋯=
0 0
𝐸𝑛 𝜓𝑛
1 0 0 1 2 0 1 1 0 2
+ 𝜆 𝐸𝑛 𝜓𝑛 + 𝐸𝑛 𝜓𝑛 + ⋯ 𝜆2 𝐸𝑛 𝜓𝑛 + 𝐸𝑛 𝜓𝑛 + 𝐸𝑛 𝜓𝑛 +⋯
Equating the coefficients of the 𝜆0 terms, we have

෡ 0 𝜓𝑛0 = 𝐸𝑛0 𝜓𝑛0
𝐻
which is the Schrodinger equation for the unperturbed problem.
෡ 0 𝜓𝑛1 − 𝐸𝑛0 𝜓𝑛1 = 𝐸𝑛1 𝜓𝑛0 − 𝐻

𝐻 ෡ ′ 𝜓𝑛0
෡ 0 𝜓𝑛1 − 𝐸𝑛0 𝜓𝑛1 = 𝑬𝒏𝟏 𝝍𝒏𝟎 − 𝐻
෡ ′ 𝝍𝒏𝟎
𝐻
𝟏 𝟎 ∗
To find𝑬𝒏 , we multiply the equation by 𝝍𝒎 and integrate over
First Order and Second Correction
all space, which gives:
𝟎 ෡0 1 0 𝟎 1 𝟏 𝟎 𝟎 𝟎 ෡′ 𝟎
𝝍𝒎 𝐻 𝜓𝑛 − 𝐸𝑛 𝝍𝒎 𝜓𝑛 = 𝑬𝒏 𝝍𝒎 𝝍𝒏 − 𝝍𝒎 𝐻 𝝍𝒏
∗ ∗
𝟎 ෡ 0 𝜓𝑛1 1 ෡ 0 𝝍𝒎𝟎 1 ෡ 0 𝝍𝒎𝟎
𝝍𝒎 𝐻 = 𝜓𝑛 𝐻 = 𝜓𝑛 𝐻
∗ ∗
1 0 𝟎 0 1 𝟎 0 𝟎 1
𝜓𝑛 𝐸𝑚 𝝍𝒎 = 𝐸𝑚 𝜓𝑛 𝝍𝒎 = 𝐸𝑚 𝝍𝒎 𝜓𝑛
at Energy
𝟎 ෡0 1 0 𝟎 1 𝟏 𝟎 𝟎 𝟎 ෡′ 𝟎
𝝍𝒎 𝐻 𝜓𝑛 − 𝐸𝑛 𝝍𝒎 𝜓𝑛 = 𝑬𝒏 𝝍𝒎 𝝍𝒏 − 𝝍𝒎 𝐻 𝝍𝒏
0 𝟎 1 0 𝟎 1 𝟏 𝟎 𝟎 𝟎 ෡′ 𝟎
𝐸𝑚 𝝍𝒎 𝜓𝑛 − 𝐸𝑛 𝝍𝒎 𝜓𝑛 = 𝑬𝒏 𝝍𝒎 𝝍𝒏 − 𝝍𝒎 𝐻 𝝍𝒏
𝟎 𝟎
𝝍𝒎 𝝍𝒏 = 𝜹𝒎𝒏
0 0 𝟎 1 𝟏 𝟎 ෡′ 𝟎
𝐸𝑚 − 𝐸𝑛 𝝍𝒎 𝜓𝑛 = 𝑬𝒏 𝛿𝑚𝑛 − 𝝍𝒎 𝐻 𝝍𝒏
If m = n
𝟏 𝟎 ෡′ 𝟎
𝑬 𝒏 = 𝝍𝒎 𝐻 𝝍𝒏
at Energy
0 𝟏 2 𝑘
𝐸𝑛 = 𝐸𝑛 + 𝜆𝑬𝒏 + 𝜆2 𝐸𝑛 + ⋯ + 𝜆𝑘 𝐸𝑛 + ⋯
First Order and Second Correction The First-Order Energy Correction
0 𝟏 2 𝑘
𝐸𝑛 = 𝐸𝑛 + 𝜆𝑬𝒏 + 𝜆2 𝐸𝑛 + ⋯ + 𝜆𝑘 𝐸𝑛 + ⋯
𝟎 ෡0 0
𝝍𝒎 𝐻 𝜓𝑛 𝟎 ෡′
𝝍𝒎 𝑯 𝝍𝒏
𝟎
at Energy
The Second-Order Energy Correction.
Equating the coefficients of the 𝜆2 terms, we get

෡ 0 𝜓𝑛0 + 𝜆 𝐻
𝐻 ෡ ′ 𝜓𝑛0 + 𝐻
෡ 0 𝜓𝑛1 ෡ 𝟎 𝝍𝒏𝟐 + 𝑯
+ 𝝀𝟐 𝑯 ෡ ′ 𝝍𝒏𝟏 +⋯=
0 0 1 0 0 1 𝟐 𝟎 𝟏 𝟏 𝟎 𝟐
𝐸𝑛 𝜓𝑛 + 𝜆 𝐸𝑛 𝜓𝑛 + 𝐸𝑛 𝜓𝑛 + ⋯ 𝝀𝟐 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 + 𝑬𝒏 𝝍𝒏 +⋯
෡ 0 𝜓𝑛2 − 𝐸𝑛0 𝜓𝑛2 = 𝑬𝒏𝟐 𝝍𝒏𝟎 + 𝐸𝑛1 𝜓𝑛1 − 𝐻

𝐻 ෡ ′ 𝜓𝑛1
𝟎 ∗
multiply the equation by 𝝍𝒎 and integrate over all space …
𝟎 ෡0 2 0 𝟎 2
𝝍𝒎 𝐻 𝜓𝑛 − 𝐸𝑛 𝝍𝒎 𝜓𝑛
at Energy
𝟐 𝟎 𝟎 1 𝟎 1 𝟎 ෡′ 1
= 𝑬𝒏 𝝍𝒎 𝝍𝒏 + 𝐸𝑛 𝝍𝒎 𝜓𝑛 − 𝝍𝒎 𝐻 𝜓𝑛
𝟎 ෡0 2 0 𝟎 2
𝝍𝒎 𝐻 𝜓𝑛 − 𝐸𝑛 𝝍𝒎 𝜓𝑛
∗ ∗
(𝟎) ෡0 (2) (2) ෡0 (𝟎) (2) ෡ 0 𝝍(𝟎)
𝝍𝒎 𝐻 𝜓𝑛 = 𝜓𝑛 𝐻 𝝍𝒎 = 𝜓𝑛 𝐻 𝒎
∗ ∗
2 0 𝟎 0 2 𝟎 0 𝟎 2
0 0 𝟎 2
𝐸𝑚 − 𝐸𝑛 𝝍𝒎 𝜓𝑛 =
𝟐 𝟎 𝟎 1 𝟎 1 𝟎 ෡′ 1
𝑬𝒏 𝝍𝒎 𝝍𝒏 + 𝐸𝑛 𝝍𝒎 𝜓𝑛 − 𝝍𝒎 𝐻 𝜓𝑛
𝟎 𝟎
at Energy
𝝍𝒎 𝝍 𝒏 = 𝜹𝒎𝒏
0 0 𝟎 2 𝟐 1 𝟎 1 𝟎 ෡′ 1
𝐸𝑚 − 𝐸𝑛 𝝍𝒎 𝜓𝑛 = 𝑬𝒏 𝛿𝑚𝑛 + 𝐸𝑛 𝝍𝒎 𝜓𝑛 − 𝝍𝒎 𝐻 𝜓𝑛
0 0 𝟎 2 𝟐 1 𝟎 1 𝟎 ෡′ 1
𝐸𝑚 − 𝐸𝑛 𝝍𝒎 𝜓𝑛 = 𝑬𝒏 𝛿𝑚𝑛 + 𝐸𝑛 𝝍𝒎 𝜓𝑛 − 𝝍𝒎 𝐻 𝜓𝑛
For m = n
𝟐 1 𝟎 1 𝟎 ෡′ 1
𝑬𝒏 = −𝐸𝑛 𝝍𝒏 𝜓𝑛 + 𝝍𝒏 𝐻 𝜓𝑛
0
𝟐 𝟎 ෡′ 1
𝑬 𝒏 = + 𝝍𝒏 𝐻 𝜓𝑛
To determine the second-order correction to the energy, we have
to know only the first-order correction to the wave function.
𝟎 ෡′ 𝟎
𝟏 𝟎
𝝍𝒏 = ෍ 𝝍𝒎
at Energy
𝟎 𝟎 𝟎 ෡′ 𝟎
𝒎≠𝒏 𝑬𝒏 − 𝑬𝒎 𝝍𝒎 𝐻 𝝍𝒏
𝟐 𝟎 ෡′ 𝟎
𝑬𝒏 = ෍ 0 0
𝝍𝒏 𝐻 𝝍𝒎
𝑚≠𝑛 𝐸𝑛 − 𝐸𝑚
The First-Order Energy Correction.
1 0 ෡′ 0
𝐸𝑛 = 𝜓𝑚 𝐻 𝜓𝑛
The Second-Order Energy Correction.
2
0 ෡′ 0
𝜓𝑚 𝐻 𝜓𝑛
2
𝐸𝑛 = ෍ 0 0
at Energy
The First-Order wavefunction Correction.
For m≠n
0 0 𝟎 𝟏 𝟏 𝟎 ෡′ 𝟎
𝐸𝑚 − 𝐸𝑛 𝝍𝒎 𝝍𝒏 = 𝑬𝒏 𝛿𝑚𝑛 − 𝝍𝒎 𝐻 𝝍𝒏
0
0 0 𝟎 𝟏 𝟎 ෡′ 𝟎
𝐸𝑚 − 𝐸𝑛 𝝍𝒎 𝝍𝒏 = − 𝝍𝒎 𝐻 𝝍𝒏
at Wavefunction
𝟏 𝟎
𝝍𝒏 = ෍ 𝑎𝑚 𝝍𝒎
𝑚
𝟏
Expanding 𝝍𝒏 in terms of the complete, orthonormal set of
(𝟎) ෡𝟎
unperturbed eigenfuctions 𝝍𝒎 of the Hermitian operator 𝑯
𝟎 𝟏
𝑎𝑚 = 𝝍𝒎 𝝍𝒏
0 0 𝟎 𝟏 𝟎 ෡′ 𝟎
First Order and Second Correction 𝐸𝑚 − 𝐸𝑛 𝝍𝒎 𝝍 𝒏 = − 𝝍𝒎 𝐻 𝝍𝒏
𝟎 𝟏
𝝍𝒎 𝝍𝒏 = 𝑎𝑚
0 0 𝟎 ෡′ 𝟎
𝐸𝑚 − 𝐸𝑛 𝑎𝑚 = − 𝝍𝒎 𝐻 𝝍𝒏 𝑚≠𝑛
𝟎 ෡′ 𝟎
𝝍𝒎 𝐻 𝝍𝒏
at Wavefunction
𝑎𝑚 = ෍ 0 0
𝑚≠𝑛
𝟎 ෡′ 𝟎
𝝍𝒎 𝐻 𝝍𝒏 The symbol σ𝑚≠𝑛 means we
𝟏 𝟎
𝝍𝒏 = ෍ 0 0
𝝍𝒎 sum over all the unperturbed
states except state n.
The First-Order Wavefunction Correction:
0 ෡′ 0
0 0
𝜓𝑛 ≈ 𝜓𝑛 + ෍ 0 0
𝜓𝑚
𝐸𝑛 − 𝐸𝑚
𝑚≠𝑛
The Second-Order Wavefunction Correction:

0 ෡′ 0
0 0
𝜓𝑛 ≈ 𝜓𝑛 + 𝜆 ෍ 0 0
𝜓𝑚 +
0 ෡′ 0 0 ෡ ′ 𝜓𝑛0
𝜓𝑚 𝐻 𝜓𝑙 𝜓𝑙 𝐻
0
+෍෍ 0 0 0 0
𝜓𝑚
at Wavefunction
𝑚≠𝑛 l≠𝑛 𝐸𝑛 − 𝐸𝑚 𝐸𝑛 − 𝐸𝑙
+𝜆2
0 ෡′ 0 0 ෡′ 0
𝜓𝑛 𝐻 𝜓𝑛 𝜓𝑚 𝐻 𝜓𝑛
0
−෍ 2 𝜓𝑚
0 0
Taken from: Sakurai, Chap 5: Time-Independent Perturbation Theory, page 292


Outline

energy level
19
Examples
1) Particle in a box with anisotropic potential
An example is the ion C≡N- in which the behavior is similar to
particle in a box, however the potential energy is slightly different
(one side is slightly higher than other side). The Hamiltonian is
Examples
Taken from: Lowe J.P and Peterson, K. A., Quantum Chemistry 3rd
Edition. Elsevier. Page 397 - 400.
ℏ2 𝑑 2 𝑉0
෡
𝐻=− + 𝑥
2𝑚 𝑑𝑥 2 𝑎
𝑉0
෡′ ≡ 𝐻
𝐻 ෡−𝐻
෡0 = 𝑥
𝑎
𝟏 (𝟎) ෡ ′ (𝟎) 𝟏 𝟎 𝑉0 𝟎
𝑬 𝒏 = 𝝍𝒏 𝐻 𝝍𝒏 𝑬 𝒏 = 𝝍𝒏 𝑥 𝝍𝒏
𝑎
1Τ2
𝟎 2 𝑛𝜋𝑥
𝝍𝒏 = 𝑠𝑒𝑛 𝑤ℎ𝑒𝑟𝑒 𝑛 = 1, 2, 3, …
𝑎 𝑎
Examples
𝟏 𝟎 𝑉0 𝟎
𝑬 𝒏 = 𝝍𝟏 𝑥 𝝍𝟏
𝑎
Nondegenerate Perturbation Theory 𝟏 𝟎 𝑉0 𝟎
𝑬 𝒏 = 𝝍𝟏 𝑥 𝝍𝟏
𝑎
𝑎
𝟏 𝟐 𝝅𝒙 𝑉0 𝝅𝒙
𝑬𝒏 = න 𝒔𝒆𝒏 𝑥 𝒔𝒆𝒏 𝑑𝑥
𝒂 0 𝒂 𝑎 𝒂
1 2 𝑉0 𝑎 1 − 𝑐𝑜𝑠2𝑏𝑥 𝜋
𝐸𝑛 = න 𝑥 𝑑𝑥 𝑏=
𝑎 𝑎 0 2 𝑎
1 2 𝑉0 𝑎 𝑥 𝑥𝑐𝑜𝑠2𝑏𝑥
𝐸𝑛 = න 𝑑𝑥 − 𝑑𝑥
𝑎 𝑎 0 2 2
𝑎
𝑎
𝑥 𝑥2 𝑎2
න 𝑑𝑥 = อ =
Examples
0 2 4 4 𝑎
𝑥𝑐𝑜𝑠2𝑏𝑥 𝑥𝑠𝑒𝑛2𝑏𝑥 𝑠𝑒𝑛2𝑏𝑥
0
න 𝑑𝑥 = −න 𝑑𝑥
0 2 2𝑏 2𝑏
𝟏 𝟎 𝑉0 𝟎
Nondegenerate Perturbation Theory 𝑬 𝒏 = 𝝍𝟏 𝑥 𝝍𝟏
𝑎
𝟏 2 𝑉0 𝑎2 𝑐𝑜𝑠2𝜋 𝑐𝑜𝑠0
𝑬𝒏 = − − +
𝑎 𝑎 4 4𝑏 2 4𝑏 2
𝟏 𝑽𝟎
𝑬𝒏 =
𝟐
0 𝑛𝜋ℏ 2 𝑛2 ℎ2
𝐸0 = =
2𝑚𝑎2 8𝑚𝑎2
𝑛2 ℎ2 𝑽𝟎
Examples
𝐸𝑛 = 2
+
8𝑚𝑎 𝟐
Nondegenerate Perturbation Theory The First-Order wavefunction Correction.
For m≠n
𝟎 ෡′ 𝟎
(1)
𝑎𝑚𝑛 = ෍ 0 0
𝑚≠𝑛
𝟎 ෡′ 𝟎
𝝍𝟐 𝐻 𝝍𝟏
(1)
𝑎21 = ෍ 0 0
𝑚≠𝑛 𝐸1 − 𝐸2
𝑎 𝟐𝝅𝒙 𝝅𝒙
‫׬‬
2 𝑉0 0 𝒔𝒆𝒏 𝑥𝒔𝒆𝒏 32𝑉0 𝑎2
(1)
𝑎21 = 𝒂 𝒂 𝑑𝑥 =
𝑎 𝑎 2
−3𝜋 /2𝑎 2 27𝜋 4
Examples
𝟎 ෡′ 𝟎
𝟏 𝟎 𝟏 32𝑉0 𝑎2 𝟎
𝝍𝒏 = ෍ 0 0
𝝍𝒎 𝝍𝟏 = 𝝍𝟐
𝐸𝑛 − 𝐸𝑚 27𝜋4
𝑚≠𝑛
Nondegenerate Perturbation Theory The First-Order energy and wavefunction corrections.
ℎ2 𝑽𝟎 𝟏 32𝑉0 𝑎2 𝟎
𝐸1 = + 𝝍𝟏 = 𝝍𝟐
2 27𝜋4
8𝑚𝑎 𝟐
Examples
Figure: Sketches of the lowest-energy wavefunction (a) before

and after perturbation and (b) the difference between them
Edition. Elsevier. Page 397 - 400.
Examples
1) Anharmonic Oscillator
ℏ2 𝑑 2 1 2
෡=−
𝐻 + 𝑘𝑥 + 𝑐𝑥 3 + 𝑑𝑥 4
2𝑚 𝑑𝑥 2 2
෡′ ≡ 𝐻
𝐻 ෡−𝐻
෡ 0 = 𝑐𝑥 3 + 𝑑𝑥 4
𝟏 𝟎 ෡′ 𝟎 𝟏 𝟎 𝟎
𝑬 𝒏 = 𝝍𝒏 𝐻 𝝍𝒏 𝑬𝒏 = 𝝍𝒏 𝑐𝑥 3 + 𝑑𝑥 4 𝝍𝒏
𝑎 1Τ4 2 Τ2
𝟎 −𝑎 𝑥
𝝍𝟎 = 𝑒 𝑤ℎ𝑒𝑟𝑒 𝑎 = 𝑚 𝑤Τℏ
𝜋
Examples
𝟏 𝟎 𝟎
𝑬𝒏 = 𝝍𝟎 𝑐𝑥 3 + 𝑑𝑥 4 𝝍𝟎
Nondegenerate Perturbation Theory 𝟏 𝟎 𝟎
𝑬𝒏 = 𝝍𝟎 𝑐𝑥 3 + 𝑑𝑥 4 𝝍𝟎
𝟏Τ 𝟒 +∞
𝟏 𝒂 𝟐
𝑬𝒏 = න 𝑐𝑥 3 + 𝑑𝑥 4 𝒆 −𝒂𝒙 𝑑𝑥
𝝅 −∞
+∞ 𝟐
The integral ‫׬‬−∞ 𝒄𝒙𝟑 𝒆−𝒂𝒙 𝒅𝒙 is odd and the result is equal to
zero. So the remain integral
𝟏Τ𝟐 +∞
𝟏 𝒂 𝟐
𝑬𝒏 = 𝟐𝒅 න 𝑥 4 𝒆−𝒂𝒙 𝑑𝑥
𝝅 0
+∞ 1Τ2
2 2𝑛 − 1 𝜋
න 𝑥 2𝑛 𝑒 −𝑏𝑥 𝑑𝑥 = 𝑛 = 1,2,3, …
0 2𝑛+1 𝑏2𝑛+1
Examples
+∞ 1Τ2 𝟏Τ𝟐
𝟐 2.2 − 1 𝜋 𝟑 𝝅
න 𝑥 4 𝒆−𝒂𝒙 𝑑𝑥 = =
0 22+1 𝑏2.2+1 𝟖 𝒂𝟓
Nondegenerate Perturbation Theory 𝟏 𝟎 𝟎
𝑬𝒏 = 𝝍𝟎 𝑐𝑥 3 + 𝑑𝑥 4 𝝍𝟎
𝟏 𝑎 1Τ2 9 𝜋 1Τ2 9 𝑎 1Τ2 3𝑑 3𝑑ℏ2

𝑬𝒏 = 2𝑑 = 2𝑑 = 2=
𝜋 8 𝑎5 8 𝑎 5 Τ 2 4𝑎 4𝑚2 𝑤 2
1 𝟑𝒅ℏ𝟐
𝐸0 = ℏ𝑤 +
2 𝟒𝒎𝟐 𝒘𝟐
Examples
Examples
3) Harmonic oscillator in the presence of external electrical field
෡′ ≡ 𝐻
𝐻 ෡−𝐻
෡ 0 = −𝑞𝐸 𝑥ො
It is well known
𝑚𝑤 𝑖 𝑝Ƹ 𝑚𝑤 𝑖 𝑝Ƹ 𝑎,
ො 𝑎ො+ = 1
𝑎ො = (𝑥ො + ቇ 𝑎ො+ = (𝑥ො − ቇ
2ℏ 𝑚𝑤 2ℏ 𝑚𝑤
1
෡0 = ℏ𝑤 𝑛 +
𝐻
2
1
Examples
෡0 |𝑛ۧ = 𝐸𝑛0 |𝑛ۧ = ℏ𝑤 𝑛 +

𝐻 |𝑛ۧ
2
0 1
𝐸𝑛 = ℏ𝑤 𝑛 +
2
First-Order Energy Correction
𝟐
𝟎 ෡′ 𝟎
0 𝟎 ෡′ 𝟎
𝐸𝑛 ≈ 𝐸𝑛 + 𝝍𝒏 𝐻 𝝍𝒏 + ෍ 𝟎 𝟎
𝒎≠𝒏 𝑬𝒏 − 𝑬 𝒎
Second-Order Energy Correction
෡′ ≡ 𝐻
𝐻 ෡−𝐻
෡ 0 = −𝑞𝐸 𝑥ො
𝟏
ෝ=
Rewriting 𝒙 ෝ+ + 𝒂
𝒂 ෝ
𝟐
Examples
First-Order Energy Correction …

𝟎 ෡′ 𝟎 −𝑞𝐸 𝟎 𝟎
𝝍𝒏 𝐻 𝝍𝒏 = 𝝍𝒏 𝑎ො+ + 𝑎ො 𝝍𝒏
2
𝟎 −𝑞𝐸
𝝍𝒏 ෡ ′ 𝝍𝒏𝟎 =
𝐻 𝝍𝒏
𝟎
𝑎ො+ 𝝍𝒏
𝟎 𝟎
+ 𝝍𝒏
𝟎
𝑎ො 𝝍𝒏
2
𝟎 −𝑞𝐸
𝝍𝒏 ෡ ′ 𝝍𝒏𝟎 =
𝐻
𝟎 0
𝑛 + 1 𝝍𝒏 𝜓𝑛+1 + 𝑛 𝝍𝒏 𝜓𝑛−1
𝟎 0
2
But we know that
0 0 1 𝑠𝑒 𝑚 = 𝑛
𝜓𝑛 𝜓𝑚 =ቊ
0 𝑠𝑒 𝑚 ≠ 𝑛
Examples
𝟏 𝟎 ෡′ 𝟎
𝑬 𝒏 = 𝝍𝒏 𝐻 𝝍𝒏 = 0
Second-Order Energy Correction …

𝟐
𝟎 ෡′ 𝟎
𝟐 𝑛+1
𝑬𝒏 = ෍ 𝟎 𝟎
𝑤ℎ𝑒𝑟𝑒 𝑚=ቊ
𝑬𝒏 − 𝑬𝒎 𝑛−1
𝒎≠𝒏
0 −𝒒𝑬 −𝒒𝑬
𝜓𝑛+1 ෝ 𝝍𝒏𝟎
ෝ+ + 𝒂
𝒂 =
0
ෝ+ 𝝍𝒏𝟎 + 𝜓𝑛+1
𝜓𝑛+1 𝒂
0
ෝ 𝝍𝒏𝟎
𝒂
𝟐 𝟐
0 −𝒒𝑬 𝟎 −𝒒𝑬 0 0
𝜓𝑛+1 ෝ+ + 𝒂
𝒂 ෝ 𝝍𝒏 = 𝒏 + 𝟏 𝜓𝑛+1 𝜓𝑛+1
𝟐 𝟐
1
0 −𝒒𝑬 𝟎 −𝒒𝑬 0
𝜓𝑛−1 ෝ+ + 𝒂
𝒂 ෝ 𝝍𝒏 = ෝ+ 𝝍𝒏𝟎 + 𝜓𝑛−1
𝜓𝑛−1 𝒂
0
ෝ 𝝍𝒏𝟎
𝒂
Examples
𝟐 𝟐
0 −𝒒𝑬 −𝒒𝑬
𝜓𝑛−1 𝒂 ෝ 𝝍𝒏𝟎
ෝ+ + 𝒂 =
0
𝒏 𝜓𝑛−1 𝜓𝑛−1
0
𝟐 𝟐
1
𝟐
𝟎 ෡′ 𝟎
𝝍𝒎 𝑯 𝝍𝒏 𝒒𝑬 𝟐 𝒒𝑬 𝟐
෍ 𝟎 𝟎
= 0 0
𝒏+𝟏 + 0 0
𝒏
𝒎≠𝒏 𝑬𝒏 − 𝑬𝒎 𝟐 𝐸𝑛 − 𝐸𝑛+1 𝟐 𝐸𝑛 − 𝐸𝑛−1
0 0
0 0 𝐸𝑛 − 𝐸𝑛+1 = 𝑛 − 𝑛 + 1
𝐸𝑛 − 𝐸𝑚 = 𝑛 − 𝑚 ቐ 0 0
𝐸𝑛 − 𝐸𝑛−1 = 𝑛 − 𝑛 − 1
𝟐
𝟎 ෡ ′ 𝝍𝒏𝟎
𝝍𝒎 𝑯 𝒒𝑬 𝟐
𝒒𝑬 𝟐
෍ 𝟎 𝟎
= 𝒏+𝟏 + 𝒏
𝑬𝒏 − 𝑬𝒎 𝟐 𝑛− 𝑛+1 𝟐 𝑛− 𝑛−1
𝒎≠𝒏
Examples
𝟐
𝟎 ෡′ 𝟎
𝝍𝒎 𝑯 𝝍𝒏 − 𝒒𝑬 𝟐
𝒒𝑬 𝟐
෍ 𝟎 𝟎
= 𝒏+𝟏 + 𝒏
𝑬𝒏 − 𝑬𝒎 𝟐 𝟐
𝒎≠𝒏
𝟐
𝟎 ෡ ′ 𝝍𝒏𝟎
𝝍𝒎 𝑯 − 𝒒𝑬 𝟐
෍ 𝟎 𝟎
=
𝑬𝒏 − 𝑬 𝒎 𝟐
𝒎≠𝒏
𝟐
𝟎 ෡′ 𝟎
0 𝟎 ෡′ 𝟎
𝐸𝑛 ≈ 𝐸𝑛 + 𝝍𝒏 𝐻 𝝍𝒏 + ෍ 𝟎 𝟎
𝒎≠𝒏 𝑬𝒏 − 𝑬𝒎
1 𝒒𝑬 𝟐
𝐸𝑛 ≈ ℏ𝑤 𝑛 + +𝟎−
2 𝟐
Examples
For m≠n
0 ෡′ 0
0 0
𝜓𝑛 ≈ 𝜓𝑛 + ෍ 0 0
𝜓𝑚
𝑚≠𝑛 𝐸𝑛 − 𝐸𝑚 𝟎 ෡′ 𝟎
𝟏 𝟎
𝝍𝒏 = ෍ 0 0
𝝍𝒎
0 −𝑞𝐸 0
𝜓𝑚 𝑎ො+ + 𝑎ො 𝜓𝑛
0 2 0
|𝜓𝑛 ۧ ≈ ฬ𝜓𝑛 ඀ + ෍ 0 0
ฬ𝜓𝑚 ඀
−𝑞𝐸 𝑛+1
Examples
0 0 0 0
|𝜓𝑛 ۧ ≈ ฬ𝜓𝑛 ඀+ 𝜓𝑛+1 𝜓𝑛+1 ฬ𝜓𝑛+1 ඀
2 2 𝑛− 𝑛+1
1
−𝑞𝐸 𝑛 0 0 0
+ 𝜓𝑛−1 𝜓𝑛−1 ฬ𝜓𝑛−1 ඀
2 2 𝑛− 𝑛−1
1
For m≠n
0 𝑞𝐸 𝑛 + 1 0 𝑞𝐸 𝑛 0
|𝜓𝑛 ۧ ≈ ฬ𝜓𝑛 ඀ + ฬ𝜓𝑛+1 ඀ − ฬ𝜓𝑛−1 ඀
2 2
0 𝑛+1 0 𝑛 0
|𝜓𝑛 ۧ ≈ ฬ𝜓𝑛 ඀ + 𝑞𝐸 ฬ𝜓𝑛+1 ඀ − 𝑞𝐸 ฬ𝜓𝑛−1 ඀
2 2
Examples
Examples
4) Hydrogen atom in the presence of external electrical field
ℏ2 2
෡=−
𝐻 𝑝Ƹ + 𝑉෠0 (𝑟) − 𝑞 𝐸 𝑧Ƹ
2𝑚
෡0
𝐻
ℏ2 2 𝑍𝑒 2
෡0
𝐻 =− ∇ − ෡′ ≡ 𝐻
𝐻 ෡−𝐻
෡ 0 = −𝑞 𝐸 𝑧Ƹ = −𝑞 𝐸 𝑟𝑐𝑜𝑠𝜃
2𝜇 𝑟
ℏ2 1 𝜕 𝜕 ෠2
𝐿
− 𝑟 2 + + ෠0 (𝑟൯ |𝑛, Λ2 , 𝑚ۧ = E|𝑛, Λ2 , 𝑚ۧ
𝑉
2𝜇 𝑟 2 𝜕𝑟 𝜕𝑟 2𝜇𝑟 2
Examples
෡ 𝐿෠2 = 0
𝐻, ෡ 𝐿෠ 𝑧 = 0
𝐻,
𝐿෠ 𝑧 |Λ2 , 𝑚ۧ = 𝑚𝑙 |Λ2 , 𝑚ۧ 𝐿෠2 |Λ2 , 𝑚ۧ = 𝑙(𝑙 + 1)|Λ2 , 𝑚ۧ

෡ 0 |𝑛, Λ2 , 𝑚ۧ = E𝑛0 |𝑛, Λ2 , 𝑚ۧ
𝐻
Considering the fundamental state for hydrogen atom

ห𝒏, 𝜦𝟐 , 𝒎ൿ = |𝟏, 𝟎, 𝟎ۧ = |𝟏𝒔ۧ
𝟐
𝟎 ෡′ 𝟎
0 𝟎 ෡′ 𝟎
𝐸𝑛 ≈ 𝐸𝑛 + 𝝍𝒏 𝑯 𝝍𝒏 + ෍ 𝟎 𝟎
𝒎≠𝒏 𝑬𝒏 − 𝑬𝒎
𝟐
0 𝒏, 𝚲𝟐 , 𝒎 ෡ ′ 𝟏𝒔
𝑯
෡ ′ 𝟏𝒔 + ෍
𝐸1𝑠 ≈ 𝐸1𝑠 + 𝟏𝒔 𝑯 𝟎 𝟎
𝑚≠𝑛 𝑬𝟏𝒔 − 𝑬𝒎
𝟐
0
෡ ′ 𝟏𝒔
𝒏, 𝚲𝟐 , 𝒎 𝑯
෡ ′ 𝟏𝒔 + 𝒒 𝑬
𝐸1𝑠 ≈ 𝐸1𝑠 − 𝒒 𝑬 𝟏𝒔 𝑯 ෍
Examples
𝟎 𝟎
𝟑Τ 𝟐
𝟏 𝟏
𝜳𝟏𝒔 (𝟏𝟎𝟎) = 𝒆 −𝒓 Τ 𝒂𝟎
𝝅𝟏Τ𝟐 𝒂𝟎
෡ ′ 𝟏𝒔
−𝒒 𝑬 𝟏𝒔 𝑯 First-Order Energy Correction
𝟏
−𝒒 𝑬 𝟏𝒔 𝒛ො 𝟏𝒔 = −𝒒 𝑬 𝟑
න𝒆−𝟐𝒓Τ𝒂𝟎 𝒓𝒄𝒐𝒔𝜽 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙
𝝅𝒂
𝟏 −𝟐𝒓Τ𝒂𝟎 3
−𝒒 𝑬 𝟏𝒔 𝒛ො 𝟏𝒔 = −𝒒 𝑬 න𝑑𝜙 න𝑐𝑜𝑠𝜃𝑠𝑒𝑛𝜃𝑑𝜃 න𝒆 𝑟 𝑑𝑟
𝝅𝒂𝟑
𝜋
𝜋 2
𝑠𝑒𝑛 𝜃
න 𝑐𝑜𝑠𝜃𝑠𝑒𝑛𝜃𝑑𝜃 = อ =0
0 2
0
𝟐
0
෡ ′ 𝟏𝒔
𝒏, 𝚲𝟐 , 𝒎 𝑯
෡ ′ 𝟏𝒔 + 𝒒 𝑬
Examples
𝐸1𝑠 ≈ 𝐸1𝑠 − 𝒒 𝑬 𝟏𝒔 𝑯 ෍ 𝟎 𝟎
0
𝟐
Nondegenerate Perturbation Theory 0 𝒏, 𝚲𝟐 , 𝒎 ෡ ′ 𝟏𝒔
𝑯
𝐸1𝑠 ≈ 𝐸1𝑠 + 𝒒 𝑬 ෍ 𝟎 𝟎
Second-Order Energy Correction
𝒏, 𝚲𝟐 , 𝒎 𝒓𝒄𝒐𝒔𝜽 𝟏𝒔 = 𝒏, 𝚲𝟐 , 𝒎 𝒓𝒄𝒐𝒔𝜽 𝟏, 𝟎, 𝟎
Examples
2𝑠 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 2,0,0 𝑟𝑐𝑜𝑠𝜃 1,0,0
2𝑠 𝑟𝑐𝑜𝑠𝜃 1𝑠 =
3 3 Τ2
1 1 1 𝑟
න𝑒 −2𝑟Τ𝑎0 𝑟𝑐𝑜𝑠𝜃 1− 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙
𝜋 𝑎 2 2𝑎0
3 3Τ2
1 1 1 𝑟4
න𝑑𝜙 න𝑐𝑜𝑠𝜃𝑠𝑒𝑛𝜃 𝑑𝜃 න𝑒 −2𝑟Τ𝑎0 𝑟3 − 𝑑𝑟
𝜋 𝑎 2 2𝑎0
𝜋
𝜋
𝑠𝑒𝑛2 𝜃
න 𝑐𝑜𝑠𝜃𝑠𝑒𝑛𝜃𝑑𝜃 = อ =0
0 2
0
Examples
2𝑠 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 0
2𝑝+1 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 2,1,1 𝑟𝑐𝑜𝑠𝜃 1,0,0
2𝑝+1 𝑟𝑐𝑜𝑠𝜃 1𝑠 =
න𝑒 −𝑟Τ𝑎0 𝑟𝑐𝑜𝑠𝜃 𝑟𝑒 −𝑟Τ2𝑎0 𝑠𝑖𝑛𝜃𝑒 +𝑖𝜙 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙
න𝑟 2 𝑒 −3𝑟Τ2𝑎0 𝑐𝑜𝑠𝜃𝑠𝑖𝑛𝜃𝑒 +𝑖𝜙 𝑟 2 𝑠𝑖𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙
න𝑒 +𝑖𝜙 𝑑𝜙 න𝑐𝑜𝑠𝜃𝑠𝑖𝑛2 𝜃𝑑𝜃 න𝑟 4 𝑒 −3𝑟Τ2𝑎0 𝑑𝑟
2𝜋
න 𝑒 +𝑖𝜙 𝑑𝜙 = 0
Examples
2𝑝+1 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 0 2𝑝−1 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 0

2𝑝0 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 2,1,0 𝑟𝑐𝑜𝑠𝜃 1,0,0
2𝑝0 𝑟𝑐𝑜𝑠𝜃 1𝑠 =
න𝑒 −𝑟Τ𝑎0 𝑟𝑐𝑜𝑠𝜃 𝑟𝑒 −𝑟Τ2𝑎0 𝑐𝑜𝑠𝜃 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙
න𝑟 2 𝑒 −3𝑟Τ2𝑎0 𝑐𝑜𝑠 2 𝜃 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙
න𝑑𝜙 න𝑐𝑜𝑠 2 𝜃𝑠𝑖𝑛𝜃𝑑𝜃 න𝑟 4 𝑒 −3𝑟Τ2𝑎0 𝑑𝑟
𝜋
2𝜋 2
න 𝑑𝜙 = 2𝜋 න 𝑐𝑜𝑠 2 𝜃𝑠𝑖𝑛𝜃𝑑𝜃 =
0 3
0
Examples
?
3𝑟
4 −2𝑎
න 𝑟 𝑒 0 𝑑𝑟
+∞
𝑛 −𝑞𝑥
𝑛!
න 𝑥 𝑒 𝑑𝑥 =
0 𝑞𝑛+1
3
Considering 𝑞 =
2𝑎0
3𝑟 5
− 4! 2
න 𝑟 4 𝑒 2𝑎0 𝑑𝑟 = 5 = 4! 𝑎05
3 3
2𝑎0
2𝑝0 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 2,1,0 𝑟𝑐𝑜𝑠𝜃 1,0,0

Examples
27 2
−𝒒 𝑬 2𝑝0 𝑟𝑐𝑜𝑠𝜃 1𝑠 = −𝒒 𝑬 𝑎0 5 = 1𝑠 𝑟𝑐𝑜𝑠𝜃 2𝑝0
3
𝟐
Nondegenerate Perturbation Theory 0
෡ ′ 𝟏𝒔
𝒏, 𝚲𝟐 , 𝒎 𝑯
𝐸1𝑠 ≈ 𝐸1𝑠 + 𝒒 𝑬 ෍ 𝟎 𝟎
2
𝟎 ෡′ 𝟎 2 2
𝝍𝒎 𝑯 𝝍𝒏 1 27 2 27 2
෍ = −𝒒 𝑬 𝒂𝟎 + −𝒒 𝑬 𝒂𝟎
𝐸𝑛
0
− 𝐸𝑚
0 0
𝐸1𝑠 −
0
𝐸2𝑝0 35 35
𝑚≠𝑛
0
𝐸1𝑠 = −13,6𝑒𝑉
0
0 𝐸1𝑠
𝐸𝑛 = 2 −13,6𝑒𝑉
𝑛 0
𝐸2𝑝0 = = −3.4𝑒𝑉
4
2,1,0 𝑟𝑐𝑜𝑠𝜃 1,0,0 2 + 1,0,0 𝑟𝑐𝑜𝑠𝜃 2,1,0 2

0
𝐸1𝑠 ≈ 𝐸1𝑠 + 0 + 0 0
Examples
𝐸1𝑠 − 𝐸2𝑝0
Examples
5) Perturbation treatment of helium atom
ground state
First Approximation
Electronic hamiltonian operator for Helium atom

Examples
Taken from: Levine, I. N., Quantum Chemistry 4th Edition. Prentice

Hall. Pages 228 – 230. 46
Examples
Error = 38%
Nondegenerate Perturbation Theory Second Approximation
Perturbation Theory. Considering the first-

order perturbation energy correction for the
helium ground state:
2 2
′ 2 ′ 2
ℏ 𝑍𝑒 ℏ 𝑍𝑒
෡𝑒0 = −
𝐻 2
∇1 − − 2
∇2 −
2𝑚𝑒 𝑟1 2𝑚𝑒 𝑟2
෡𝑒0 = 𝐻
𝐻 ෡10 + 𝐻
෡20 Sum of two hydrogenlike
Hamiltonians, one for each electron
𝑒′2
෡𝑒′
𝐻 =+ Perturbative term
𝑟12
Examples
𝟏 𝟎 ෡′ 𝟎
𝑬 = 𝝍𝟏𝒔 𝐻𝑒 𝝍 𝟏𝒔 𝟑Τ𝟐
𝟏 𝒁𝟏
𝜳𝟏𝒔 (𝟏𝟎𝟎) = 𝒆−𝒁𝟏 𝒓Τ𝒂𝟎
𝝅 𝟏Τ 𝟐 𝒂𝟎
2
Nondegenerate Perturbation Theory 0
𝜓1𝑠2 𝑞1 , 𝑞2 = ෑ 𝜙𝑖 𝑞𝑖 = 𝜙1 𝑞1 𝜙2 𝑞2
𝑖=1
3Τ 2 2 𝑍
0 1 𝑍 −𝑎 (𝑟1 +𝑟2 )
𝜓1𝑠2 𝑞1 , 𝑞2 = 𝑒 0
𝜋 1Τ2 𝑎0
𝟔
𝟎 𝟎 𝟏 𝒁 −
𝒁
(𝒓 +𝒓 ቁ 𝒆′𝟐 −𝒂𝒁 (𝒓𝟏 +𝒓𝟐 ቁ
𝝍𝟏𝒔 ෡ ′𝒆 𝝍𝟏𝒔
𝑯 = 𝟐 න 𝒆 𝒂𝟎 𝟏 𝟐 𝒆 𝟎 𝑑𝜏1 𝑑𝜏2
𝝅 𝒂𝟎 𝒓𝟏𝟐
𝟔 2𝜋 2𝜋 𝜋 𝜋 ∞ ∞
𝒆′𝟐 𝒁 𝟐𝒁𝒓 𝟐𝒁𝒓
− 𝒂 𝟏 − 𝒂 𝟐 𝟏 2 2
= න 𝑑𝜙1 න 𝑑𝜙2 න 𝑠𝑒𝑛𝜃1 𝑑𝜃1 න 𝑠𝑒𝑛𝜃2 𝑑𝜃2 න න 𝒆 𝟎 𝒆 𝟎 𝑟 𝑟 𝑑𝑟 𝑑𝑟
𝝅𝟐 𝒂𝟎 𝒓𝟏𝟐 1 2 1 2
0 0 0 0 0 0
Examples
2𝜋 𝜋 𝜋
න 𝑑𝜙 = 2𝜋 න 𝑠𝑒𝑛𝜃𝑑𝜃 = −𝑐𝑜𝑠𝜃ቚ = −𝑐𝑜𝑠𝜋 − −𝑐𝑜𝑠0 = 2
0 0
0
Nondegenerate Perturbation Theory 𝟐𝒁𝒓
− 𝒂 𝟐
𝟎 ෡′ 𝟎 16𝑍 6 𝑒′2 𝟐𝒁𝒓𝟏
− 𝒂 2
𝒆 𝟎 2
𝝍𝟏𝒔 𝑯 𝒆 𝝍 𝟏𝒔 = න 𝒆 𝟎 𝑟1 𝑑𝑟1 න 𝑟 𝑑𝑟
𝑎06 𝒓𝟏𝟐 2 2
𝟎 16𝑍 6 𝑒′2 −
𝟐𝒁𝒓𝟏
𝝍𝟏𝒔 ෡ ′𝒆 𝝍𝟏𝒔𝟎
𝑯 = න 𝒆 𝒂𝟎 𝑟 2 𝑑𝑟 𝐵
1 1
𝑎06
𝑟1 ∞
1 2𝑍𝑟2 2𝑍𝑟2
2 − 𝑎0 −
𝑎0 𝑑𝑟
𝐵= න 𝑟2 𝑒 𝑑𝑟2 + න 𝑟2 𝑒 2
𝑟1
0 𝑟1
𝑥 2 2𝑥 2
න𝑥 2 𝑒 −𝑏𝑥 𝑑𝑥 = −𝑒 −𝑏𝑥 + 2+ 3
Examples
𝑏 𝑏 𝑏 𝑒 −𝑏𝑥
න𝑥𝑒 −𝑏𝑥 𝑑𝑥 = − 2 𝑏𝑥 + 1
𝑏
Acosta, C. R., Tapia, J. A., Cab, “Restricted Closed Shell Hartree Fock Roothaan Matrix
Method Applied to Helium Atom using Mathematica”. Eur. J. Phys. Ed. 5, 1 – 14 (2014).
Nondegenerate Perturbation Theory 1 2𝑍𝑟1 2
𝑟2 𝑎0 2𝑟2 𝑎02 2𝑎03
𝑟1
𝑎02 𝑒 −2𝑍𝑥 2𝑍
∞
−
𝐵= −𝑒 𝑎0 + + อ − 𝑟 +1 อ
𝑟1 2𝑍 2𝑍 2 2𝑍 3 2𝑍 2 𝑎0 1
0 𝑟1
𝑎03 2𝑍𝑟
− 𝑎 1 𝑎02 𝑎03
𝐵 = + 3 −𝑒 0 +
4𝑍 𝑟1 4𝑍 2 4𝑍 3 𝑟1
0 16𝑍 6 𝑒′2 2𝑍𝑟

− 𝑎 1 2 𝑎03 𝑎 2
0 𝑎 3
0
𝜓1𝑠 ෡𝑒′ 𝜓1𝑠0
𝐻 = න 𝑒 0 𝑟1 𝑑𝑟1 + 3 − 𝑒 −2𝑍𝑟1 +
6 4𝑍 𝑟1 4𝑍 2 4𝑍 3 𝑟1
𝑎0
0 ෡′ 0
𝜓1𝑠 𝐻𝑒 𝜓1𝑠
2𝑍𝑟 2𝑍𝑟
6 2 − 𝑎 1 2 2𝑍𝑟1 − 𝑎 1 2
16𝑍 𝑒′ ൥ 𝑒 0 𝑟1 − 𝑒 0 𝑟1
Examples
3
= න 𝑎0 𝑑𝑟1 − 𝑎02 න 𝑒 𝑎0 𝑑𝑟1
𝑎06 4𝑍 3 𝑟1 4𝑍 2
2𝑍𝑟1
−
2𝑍𝑟1 𝑒 𝑎0 𝑟 2
− 1 ൩
− 𝑎03 න 𝑒 𝑎0 𝑑𝑟1
4𝑍 3 𝑟1
0 16𝑍 6 𝑒′2 𝑎05 1 1
𝐻 = 1− −
16𝑎06 8 4
0 𝑍 6 𝑒′2 8 − 1 − 2 5 𝑍 6 𝑒′2
𝐻 = =
𝑎0 8 8 𝑎0
0 5 𝑍 6 𝑒′2 10
𝐻 = = 13,606 = 34,0𝑒𝑉
8 𝑎0 4
2
0 2 2
𝑒′
𝐸1𝑠 2 = −𝑍 = −108,8𝑒𝑉
2𝑎0
Examples
0 ′
𝐸1𝑠 2 + 𝐸 = −108,8 + 34,0 = −74,8𝑒𝑉
Which, compared with the experimental value of – 79,0 eV, is in

error by 5,3%.
Examples
Edition. Elsevier. Page 405.

Outline

energy level
54
෡ 0 𝜓𝑛0 = 𝐸𝑛0 𝜓𝑛0
𝐻
Unperturbed Schrödinger equation
Degenerate Perturbation Theory
0 0 0 0
𝐸1 = 𝐸2 = 𝐸3 = ⋯ = 𝐸𝑑
where d indicates the degree of degeneracy.
෡ 𝑛= 𝐻
𝐻𝜓 ෡ 0 +𝜆𝐻
෡ ′ 𝜓𝑛 = 𝐸𝑛 𝜓𝑛
perturbed wave function
Taken from: Levine, I. N., Quantum Chemistry Effect of a perturbation

4th Edition. Prentice Hall. Pages 228 – 230. on energy levels.
0
If 𝐸𝑛 is the eigenvalue of the d-fold degenerate level, any
linear combination
0 0 0
𝑐1 𝜓1 + 𝑐2 𝜓2 + ⋯ + 𝑐𝑑 𝜓𝑑
is also solution of the unperturbed Hamiltonian with eigenvalue
0 0 0 𝟎
𝐸1 = 𝐸2 = 𝐸3 = ⋯ = 𝑬𝒅
As done as previously:
0 1 2
𝜓𝑛 = 𝜙𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯ 𝑛 = 1, 2, … 𝑑
𝟎 1 2
𝐸𝑛 = 𝑬𝒅 + 𝜆𝐸𝑛 + 𝜆2 𝐸𝑛 + … 𝑛 = 1, 2, … 𝑑
෡ 0 +𝜆𝐻
෡′ 0 1 2
𝐻 𝜙𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯
𝟎 1 2 0 1 2
= 𝑬𝒅 + 𝜆𝐸𝑛 + 𝜆2 𝐸𝑛 + ⋯ 𝜙𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯
෡ 0 +𝜆𝐻
෡′ 0 1 2
𝐻 𝜙𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯
𝟎 1 2 0 1 2
= 𝑬𝒅 + 𝜆𝐸𝑛 + 𝜆2 𝐸𝑛 + ⋯ 𝜙𝑛 + 𝜆𝜓𝑛 + 𝜆2 𝜓𝑛 + ⋯

෡ 0 𝜓𝑛0 = 𝑬𝒅𝟎 𝜙𝑛0
𝐻
෡ 0 𝜓𝑛1 − 𝑬𝒅𝟎 𝜓𝑛1 = 𝐸𝑛1 𝜙𝑛0 − 𝐻

𝐻 ෡ ′ 𝜙𝑛0 𝑛 = 1, 2, … 𝑑
𝟎 ∗
We now multiply the equation by 𝝍𝒎and integrate over all
space, where m is one of the states corresponding to the d-fold
degenerate unperturbed level under consideration; that is 1  m 
d. We get …
𝟎 ෡0 1 𝟎 𝟎 1 𝟏 𝟎 0 𝟎 ෡′ 0
𝝍𝒎 𝐻 𝜓𝑛 − 𝑬𝒅 𝝍𝒎 𝜓𝑛 = 𝑬𝒏 𝝍𝒎 𝜙𝑛 − 𝝍𝒎 𝐻 𝜙𝑛
∗ ∗
𝟎 ෡ 0 𝜓𝑛1 1 ෡ 0 𝝍𝒎𝟎 1 ෡ 0 𝝍𝒎𝟎
𝝍𝒎 𝐻 = 𝜓𝑛 𝐻 = 𝜓𝑛 𝐻
∗ ∗
1 0 𝟎 0 1 𝟎 0 𝟎 1
For 1  m  d: 0 𝟎 0 0 0 𝟎
𝐸𝑚 = 𝑬𝒅 𝐸1 = 𝐸2 = 𝐸3 = ⋯ = 𝑬𝒅
𝟎 ෡′ 0 𝟏 𝟎 0
𝝍𝒎 𝐻 𝜙𝑛 − 𝑬𝒏 𝝍𝒎 𝜙𝑛 = 0 𝑚 = 1, 2, … 𝑑
𝑑
0 (0)
𝜙𝑛 = lim 𝜓𝑛 = ෍ 𝑐𝑖 𝜓𝑖 1≤𝑛 ≤𝑑
𝜆→0
𝑖=1
𝑑 𝒅
𝟎 ෡′ 𝟎 𝟏 𝟎 𝟎
෍ 𝑐𝑖 𝝍𝒎 𝐻 𝝍𝒊 − 𝑬𝒏 ෍ 𝑐𝑖 𝝍𝒎 𝝍𝒊 = 0
𝑖=1 𝒊=𝟏
𝟎 𝟎
𝝍𝒎 𝝍 𝒊 = 𝛿𝑚𝑖
𝑑
𝟎 ෡′ 𝟎 𝟏
෍ 𝝍𝒎 𝐻 𝝍𝒊 − 𝑬𝒏 𝛿𝑚𝑖 𝑐𝑖 = 0 𝑚 = 1, 2, … 𝑑
𝑖=1
This is a set of d linear, homogeneous equation in the d unknowns c’s

coefficients, which are the coefficients in the correct zeroth-order wave
0
function 𝜙𝑛
For nontrivial solutions, the determinant of the coefficients must vanish

𝑑
𝟎 ෡′ 𝟎 𝟏
෍ 𝝍𝒎 𝐻 𝝍𝒊 − 𝑬𝒏 𝛿𝑚𝑖 𝑐𝑖 = 0 𝑚 = 1, 2, … 𝑑
𝑖=1
𝟎 ෡′ 𝟎 𝟏
𝑑𝑒𝑡 𝝍𝒎 𝐻 𝝍𝒊 − 𝑬𝒏 𝛿𝑚𝑖 = 0
(1) ′ ′
𝐻11 − 𝐸𝑛 𝐻12 … 𝐻1𝑑
′ ′ (1) ′
𝐻21 𝐻22 − 𝐸𝑛 … 𝐻2𝑑 =0
… … … …
′ ′ ′ (1)
𝐻𝑑1 𝐻𝑑2 … 𝐻𝑑𝑑 − 𝐸𝑛
As an example, consider the effect of a perturbation H’ on

the lowest degenerate energy level of a particle in a cubic
box. We have three states corresponding to this level:
𝟎 𝟎 𝟎
𝝍𝟐𝟏𝟏 , 𝝍𝟏𝟐𝟏 , 𝝍𝟏𝟏𝟐 .
Degenerate Perturbation Theory Particle in a cubic box
Electron energy:
 h2  2  h2  2  h2  2
Enx,ny ,nz =  n +  n y +  nz
2  x  8mL 
2  8mL 
2
 8mLx   y   z 
Particle trapped in a
tridimensional box in
2 
h  nx
2
n
2
n
2 
z  which its potential
Enx ,ny ,nz = + +
y
Particle in a cubic box
8m  Lx 2 Ly 2 Lz 2  energy V = ∞ outside
the box
nx , n y , nz = 1,2,3...
61
Degenerate Perturbation Theory Particle in a cubic box
ℎ2 2 2 2
𝐸𝑡𝑜𝑡𝑎𝑙 = 𝑛𝑋 + 𝑛 𝑌 + 𝑛 𝑍
8𝑚𝐿2
nx ny nz E (h2/8mL2)
1 1 1 3
2 1 1 6
1 2 1 6
1 1 2 6
2 2 1 9
2 1 2 9
1 2 2 9
50 level 2 2 2 12
62
Caixa Tridimensional
These unperturbed wave functions are orthonormal, and the secular
equation is:
෡ ′ 211 − 𝐸𝑛(1)
211 𝐻 211 𝐻෡ ′ 121 ෡ ′ 112
211 𝐻
121 𝐻෡ ′ 211 ෡ ′ 121 − 𝐸𝑛(1)
121 𝐻 ෡ ′ 112
121 𝐻 =0
෡ ′ 211
112 𝐻 ෡ ′ 121
112 𝐻 ෡ ′ 112 − 𝐸𝑛(1)
112 𝐻
Consider the perturbation as

𝑎
𝑉 0<𝑥< 𝑎𝑛𝑑 0 < 𝑦 < 𝑎/2
𝐻′ = ቐ 0 2
0 𝑜𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒
𝟎 𝟐 𝟑/𝟐 𝒏 𝝅 𝒏𝒚 𝝅 𝒏𝒛 𝝅
𝝍𝒏𝒙,𝒏𝒚,𝒏𝒛 = 𝒔𝒊𝒏 𝒙 𝒙 𝒔𝒊𝒏 𝒚 𝒔𝒊𝒏 𝒛
𝒂 𝒂 𝒂 𝒂
The first-order correction to the ground state energy is given
by:
𝟎 ෡′ 𝟎 𝟏
𝟎 ෡′ 𝟎 𝟏
𝝍𝟏𝟏𝟏 𝐻 𝝍𝟏𝟏𝟏 − 𝑬𝟎 𝛿11 = 0
𝟏 𝟐 𝟑 𝒂/𝟐 𝝅 𝒂/𝟐 𝝅 𝒂 𝝅
𝑬𝟎 = 𝑽𝟎 ‫𝒙 𝟐𝒏𝒊𝒔 𝟎׬‬ 𝒅𝒙 ‫𝟎׬‬ 𝒔𝒊𝒏𝟐 𝒚 𝒅𝒚 ‫𝟐𝒏𝒊𝒔 𝟎׬‬ 𝒛 𝒅𝒛
𝒂 𝒂 𝒂 𝒂
𝟏 𝑽𝟎
𝑬𝟎 =
𝟒
෡ ′ 211 − 𝐸𝑛(1)
211 𝐻 211 𝐻෡ ′ 121 ෡ ′ 112
211 𝐻
121 𝐻෡ ′ 211 ෡ ′ 121 − 𝐸𝑛(1)
121 𝐻 ෡ ′ 112
121 𝐻 =0
෡ ′ 211
112 𝐻 ෡ ′ 121
112 𝐻 ෡ ′ 112 − 𝐸𝑛(1)
112 𝐻
𝟎 𝟐 𝟑/𝟐 𝟐𝝅 𝝅 𝝅
𝝍𝟐𝟏𝟏 = 𝒔𝒊𝒏 𝒙 𝒔𝒊𝒏 𝒚 𝒔𝒊𝒏 𝒛
𝒂 𝒂 𝒂 𝒂
𝟎 𝟐 𝟑/𝟐 𝝅 𝟐𝝅 𝝅
𝝍𝟏𝟐𝟏 = 𝒔𝒊𝒏 𝒙 𝒔𝒊𝒏 𝒚 𝒔𝒊𝒏 𝒛
𝒂 𝒂 𝒂 𝒂
𝟎 𝟐 𝟑/𝟐 𝝅 𝝅 𝟐𝝅
𝝍𝟏𝟏𝟐 = 𝒔𝒊𝒏 𝒙 𝒔𝒊𝒏 𝒚 𝒔𝒊𝒏 𝒛
𝒂 𝒂 𝒂 𝒂
෡ ′ 211 =
211 𝐻
𝟑 𝒂/𝟐 𝒂/𝟐 𝒂
𝟐 𝟐𝝅 𝝅 𝝅
𝑽𝟎 න 𝒔𝒊𝒏𝟐 𝒙 𝒅𝒙 න 𝒔𝒊𝒏 𝟐
𝒚 𝒅𝒚 න 𝒔𝒊𝒏 𝟐
𝒛 𝒅𝒛
𝒂 𝟎 𝒂 𝟎 𝒂 𝟎 𝒂
෡ ′ 211 = 𝑽𝟎 = 121 𝐻
211 𝐻 ෡ ′ 121 = 112 𝐻
෡ ′ 122
𝟒
𝟑 𝒂/𝟐
𝟐 𝟐𝝅 𝝅
෡ ′ 121 =
211 𝐻 𝑽𝟎 න 𝒔𝒊𝒏 𝒙 𝒔𝒊𝒏 𝒙 𝒅𝒙

𝒂 𝒂 𝒂
𝟎
𝒂/𝟐
𝒂
𝝅 𝟐𝝅 𝝅
න 𝒔𝒊𝒏 𝒚 𝒔𝒊𝒏 𝒚 𝒅𝒚 න 𝒔𝒊𝒏𝟐 𝒛 𝒅𝒛
𝒂 𝒂 𝟎 𝒂
𝟎
16
෡ ′ 121 =
211 𝐻 𝑽 = 121 ෡
𝐻 ′ 211
9𝜋 2 𝟎
𝟑 𝒂/𝟐
𝟐 𝟐𝝅 𝝅
෡ ′ 112 =
211 𝐻 𝑽𝟎 න 𝒔𝒊𝒏 𝒙 𝒔𝒊𝒏 𝒙 𝒅𝒙
𝒂 𝒂 𝒂
𝟎
𝒂/𝟐
𝒂
𝝅 𝝅 𝟐𝝅
න 𝒔𝒊𝒏𝟐 𝒚 𝒅𝒚 න 𝒔𝒊𝒏 𝒛 𝒔𝒊𝒏 𝒛 𝒅𝒛
𝒂 𝟎 𝒂 𝒂
𝟎
෡ ′ 112 = 0 = 112 𝐻
211 𝐻 ෡ ′ 121
𝑽𝟎 (1) 16
− 𝐸𝑛 𝑽 0
𝟒 9𝜋 2 𝟎
16 𝑽𝟎 (1)
𝑽 − 𝐸𝑛 0 =0
9𝜋 2 𝟎 𝟒
𝑽𝟎 (1)
0 0 − 𝐸𝑛
𝟒
𝑽𝟎 (1) 16
− 𝐸𝑛 𝑽 0
𝟒 9𝜋 2 𝟎
16 𝑽𝟎 (1)
𝑽 − 𝐸𝑛 0 =0
9𝜋 2 𝟎 𝟒
𝑽𝟎 (1)
0 0 − 𝐸𝑛
𝟒
3 2
𝑽𝟎 (1) 16 𝑽𝟎 1
− 𝐸𝑛 − 𝑽 − 𝐸𝑛 =0
𝟒 9𝜋 2 𝟎 𝟒
𝑽𝟎
(1)
(1) 𝑽𝟎 16 𝐸1 =
𝐸𝑛 = ∓ 𝑽 𝟒
𝟒 9𝜋 2 𝟎
2
(1) 𝑽𝟎 8
2 𝐸2 = 𝟏+
(1) 𝑽𝟎 8 𝟒 3𝜋
𝐸𝑛 = 𝟏∓ = 2
𝟒 3𝜋 (1) 𝑽𝟎 8
𝐸3 = 𝟏−
𝟒 3𝜋
𝑽𝟎
𝐸10 + 𝜆
𝟒
2
0
8 𝑽𝟎 3ℎ 2
𝐸1 𝜆 = 𝐸1 + 𝜆 𝟏 + 3𝜋 𝟒 𝐸10 =
8𝑚𝑎2
2
8 𝑽𝟎
𝐸10 + 𝜆 𝟏 −
3𝜋 𝟒
𝑎
𝑉 0<𝑥< 𝑎𝑛𝑑 0 < 𝑦 < 𝑎/2
𝐻′ = ቐ 0 2
0 𝑜𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒
Degenerate Perturbation Theory Perturbation treatment of the first excited states of Helium
As a result of perturbation theory to the ground state of the

helium atom:
First excited states of helium
The lowest unperturbed excited states have n1 = 1, n2 =2 or

n1 =2, n2 =1.
2
5 𝑍2𝑒′
𝐸𝐻𝑒 =− = −68,03,0𝑒𝑉
8 𝑎0
Taken from: Levine, I. N., Quantum Chemistry
4th Edition. Prentice Hall. Pages 228 – 230.
The eight unperturbed wave functions are:
𝟎 𝟎
𝝍𝟏 = 1s 1 2s(2) 𝝍𝟓 = 1s 1 2𝑝𝑦 (2)
𝟎 𝟎
𝝍𝟐 = 2s 1 1s(2) 𝝍𝟔 = 2𝑝𝑦 1 1s(2)
𝟎 𝟎
𝝍𝟑 = 1s 1 2𝑝𝑥 (2) 𝝍𝟕 = 1s 1 2𝑝𝑧 (2)
𝟎 𝟎
𝝍𝟒 = 2𝑝𝑥 1 1s(2) 𝝍𝟖 = 2𝑝𝑧 1 1s(2)
𝟎 ෡′ 𝟎 𝟏
(1) ′ ′
𝐻11 − 𝐸𝑛 𝐻12 … 𝐻1𝑑
′ 2
′
𝐻21 ′ (1) ′ 𝑒
𝐻22 − 𝐸𝑛 … 𝐻2𝑑=0 ෡′ =
𝐻
… … … … 𝑟12
′ ′ ′ (1)
𝐻𝑑1 𝐻𝑑2 … 𝐻𝑑𝑑 − 𝐸𝑛


(1) ′ ′
𝐻11 − 𝐸𝑛 𝐻12 … 𝐻1𝑑
′ ′ (1) ′
2 𝐻21 𝐻22 − 𝐸𝑛 … 𝐻2𝑑 =0
𝑒′ … … … …
𝐻11 = න 1s 1 ∗ 2s(2)∗ 1s 1 2s(2)𝑑𝑣 ′
𝐻𝑑1 ′
𝐻𝑑2 ′
… 𝐻𝑑𝑑
(1)
− 𝐸𝑛
𝑟12
2
′
𝑒
𝐻11 = න 1s 1 2 2s 2 2
𝑑𝑣 = 𝐽1𝑠2𝑠
𝑟12
Coulomb Integral
′ 2
′
𝑒
𝐻12 = න 1s 1 ∗ 2s(2)∗ 2s 1 1s(2)𝑑𝑣 = 𝐾1𝑠2𝑠
𝑟12
𝑒 ′2
′
𝐻34 = න 1s 1 ∗ 2𝑝𝑥 (2)∗ 2𝑝𝑥 1 1s(2)𝑑𝑣 = 𝐾1𝑠2𝑝𝑥
𝑟12
′2 Exchange Integrals
′ 𝑒
𝐻56 = න 1s 1 ∗ 2𝑝𝑦 (2)∗ 2𝑝 1 1s(2)𝑑𝑣 = 𝐾1𝑠2𝑝𝑦
𝑟12 𝑦
𝑒 ′2
′
𝐻78 = න 1s 1 ∗ 2𝑝𝑧 (2)∗ 2𝑝𝑧 1 1s(2)𝑑𝑣 = 𝐾1𝑠2𝑝𝑧
𝑟12

(1) ′ ′
𝐻11 − 𝐸𝑛 𝐻12 … 𝐻1𝑑
′ ′ (1) ′
𝐻21 𝐻22 − 𝐸𝑛 … 𝐻2𝑑 =0
… … … …
′ ′ ′ (1)
2 𝐻𝑑1 𝐻𝑑2 … 𝐻𝑑𝑑 − 𝐸𝑛
′
𝑒′
𝐻13 = න 1s 1 ∗ 2s(2)∗ 1s 1 2𝑝𝑥 (2)𝑑𝑣 = 0
𝑟12
2
′ ∗ ∗
𝑒′
𝐻14 = න 1s 1 2s(2) 2𝑝 1 1s(2)𝑑𝑣 = 0
𝑟12 𝑥
2
𝑒 ′
′ ∗ 2s(2)∗
𝐻15 = න 1s 1 1s 1 2𝑝𝑦 (2)𝑑𝑣 = 0
𝑟12
′2
′ ∗ 2s(2)∗
𝑒
𝐻16 = න 1s 1 2𝑝 1 1s(2)𝑑𝑣 = 0
𝑟12 𝑦
𝑒 ′2
′ ∗ 2s(2)∗
𝐻17 = න 1s 1 1s 1 2𝑝𝑧 (2)𝑑𝑣 = 0
𝑟12
𝑒 ′2
′ ∗ 2s(2)∗
𝐻18 = න 1s 1 2𝑝 1 1s(2)𝑑𝑣 = 0
𝑟12 𝑧
𝑒 ′2
′ ∗ 2𝑝 (2)∗
𝐻35 = න 1s 1 𝑥 1s 1 2𝑝𝑦 (2)𝑑𝑣 = 0
𝑟12
′ ′
− 𝐸 (1) 𝐻12
𝐻11 0 0 0 0 0 0
′ ′
𝐻21 𝐻22 − 𝐸 (1) 0 0 0 0 0 0
′ ′
0 0 𝐻33 − 𝐸 (1) 𝐻34 0 0 0 0
′ ′
0 0 𝐻43 𝐻44 − 𝐸 (1) 0 0 0 0
′ (1) ′ =0
0 0 0 0 𝐻55 − 𝐸 𝐻56 0 0
′ ′
0 0 0 0 𝐻65 𝐻66 − 𝐸 (1) 0 0
′ ′
0 0 0 0 0 0 𝐻77 − 𝐸 (1) 𝐻78
′ ′
0 0 0 0 0 0 𝐻87 𝐻88 − 𝐸 (1)
The secular determinant is in block-diagonal form and

factors into four determinants, each of second order. We
conclude that the correct zeroth-order functions have the
form

′ ′
𝐻11 − 𝐸 (1) 𝐻12 0 0 0 0 0 0
′ ′
𝑑 𝐻21 𝐻22 − 𝐸 (1) 0 0 0 0 0 0
′ ′
0 (0) 0 0 𝐻33 − 𝐸 (1) 𝐻34 0 0 0 0
𝜙𝑛 = lim 𝜓𝑛 = ෍ 𝑐𝑖 𝜓𝑖 1≤𝑛 ≤𝑑 ′
0 0 𝐻43 𝐻44 − 𝐸 ′ (1)
0 0 0 0
𝜆→0 =0
𝑖=1 0 0 0 0 𝐻55 − 𝐸 ′ (1) ′
𝐻56 0 0
′ ′
0 0 0 0 𝐻65 𝐻66 − 𝐸 (1) 0 0
′ ′
0 0 0 0 0 0 𝐻77 − 𝐸 (1) 𝐻78
′ ′
0 (0) (0) 0 0 0 0 0 0 𝐻87 𝐻88 − 𝐸 (1)
𝜙1 = 𝑐1 𝜓1 + 𝑐2 𝜓2 ′ ′
𝐻11 − 𝐸 (1) 𝐻12
0 (0) (0) ′ ′
=0
𝜙2 = 𝑐ഥ1 𝜓1 + 𝑐ഥ2 𝜓2 𝐻21 𝐻22 − 𝐸 (1)
0 (0) (0)
𝜙3 = 𝑐3 𝜓3 + 𝑐4 𝜓4 ′ ′
𝐻33 − 𝐸 (1) 𝐻34
0 (0) (0) ′ ′
=0
𝜙4 = 𝑐ഥ3 𝜓3 + 𝑐ഥ4 𝜓4 𝐻43 𝐻44 − 𝐸 (1)
0 (0) (0)
𝜙5 = 𝑐5 𝜓5 + 𝑐6 𝜓6 ′ ′
𝐻55 − 𝐸 (1) 𝐻56
0 (0) (0) ′ ′ (1)
=0
𝜙6 = 𝑐ഥ5 𝜓5 + 𝑐ഥ6 𝜓6 𝐻65 𝐻66 − 𝐸
0 (0) (0)
𝜙7 = 𝑐7 𝜓7 + 𝑐8 𝜓8 ′ ′
𝐻77 − 𝐸 (1) 𝐻78
0 (0) (0) ′ ′ (1)
=0
𝜙8 = 𝑐ഥ7 𝜓7 + 𝑐ഥ8 𝜓8 𝐻87 𝐻88 − 𝐸
′ ′ ′ ′
𝐻11 − 𝐸 (1) 𝐻12 ′
𝐻33 − 𝐸 (1) ′
𝐻34 𝐻55 − 𝐸 (1) 𝐻56 ′
𝐻77 − 𝐸 (1) ′
𝐻78
′ ′
=0 =0 =0 =0
𝐻21 𝐻22 − 𝐸 (1) ′
𝐻43 ′
𝐻44 − 𝐸 (1) ′
𝐻65 ′
𝐻66 − 𝐸 (1) ′
𝐻87 ′
𝐻88 − 𝐸 (1)
𝐽1𝑠2𝑠 − 𝐸 (1) 𝐾1𝑠2𝑠 𝐽1𝑠2𝑝𝑥 − 𝐸 (1) 𝐾1𝑠2𝑝𝑥

=0 =0
𝐾1𝑠2𝑠 𝐽1𝑠2𝑠 − 𝐸 (1) 𝐾1𝑠2𝑝𝑥 𝐽1𝑠2𝑝𝑥 − 𝐸 (1)
𝐽1𝑠2𝑝𝑦 − 𝐸 (1) 𝐾1𝑠2𝑝𝑦 𝐽1𝑠2𝑝𝑧 − 𝐸 (1) 𝐾1𝑠2𝑝𝑧

=0 =0
𝐾1𝑠2𝑝𝑦 𝐽1𝑠2𝑝𝑦 − 𝐸 (1) 𝐽1𝑠2𝑝𝑧 − 𝐸 (1)
𝐾1𝑠2𝑝𝑧
(1) (1)
𝐸1 = 𝐽1𝑠2𝑠 − 𝐾1𝑠2𝑠 𝐸5 = 𝐽1𝑠2𝑝𝑦 − 𝐾1𝑠2𝑝𝑦
(1) (1)
𝐸2 = 𝐽1𝑠2𝑠 + 𝐾1𝑠2𝑠 𝐸6 = 𝐽1𝑠2𝑝𝑦 + 𝐾1𝑠2𝑝𝑦
(1) (1)
𝐸3 = 𝐽1𝑠2𝑝𝑥 − 𝐾1𝑠2𝑝𝑥 𝐸7 = 𝐽1𝑠2𝑝𝑧 − 𝐾1𝑠2𝑝𝑧
(1) (1)
𝐸4 = 𝐽1𝑠2𝑝𝑥 + 𝐾1𝑠2𝑝𝑥 𝐸8 = 𝐽1𝑠2𝑝𝑧 + 𝐾1𝑠2𝑝𝑧
(1) (1) (1) (1) (1) (1)

𝐸3 = 𝐸5 = 𝐸7 𝐸4 = 𝐸6 = 𝐸8
Taken from: Levine, I. N., Quantum Chemistry 4th Edition. Prentice Hall. Pages 228 – 230.
𝐽1𝑠2𝑠 = 11,42 𝑒𝑉
Coulomb Integrals
𝐽1𝑠2𝑝𝑥 = 𝐽1𝑠2𝑝𝑦 = 𝐽1𝑠2𝑝𝑧 = 13,21𝑒𝑉
𝐾1𝑠2𝑠 = 1,19𝑒𝑉
Exchange Integrals
𝐾1𝑠2𝑝𝑥 = 𝐾1𝑠2𝑝𝑦 = 𝐾1𝑠2𝑝𝑧 = 0,93𝑒𝑉
(1) (1)
𝐸1 = 𝐽1𝑠2𝑠 − 𝐾1𝑠2𝑠 = 10,23𝑒𝑉 𝐸5 = 𝐽1𝑠2𝑝𝑦 − 𝐾1𝑠2𝑝𝑦 = 12,28𝑒𝑉
(1) (1)
𝐸2 = 𝐽1𝑠2𝑠 + 𝐾1𝑠2𝑠 = 12,61𝑒𝑉 𝐸6 = 𝐽1𝑠2𝑝𝑦 + 𝐾1𝑠2𝑝𝑦 = 14,14𝑒𝑉
(1) (1)
𝐸3 = 𝐽1𝑠2𝑝𝑥 − 𝐾1𝑠2𝑝𝑥 = 12,28𝑒𝑉 𝐸7 = 𝐽1𝑠2𝑝𝑧 − 𝐾1𝑠2𝑝𝑧 = 12,28𝑒𝑉
(1) (1)
𝐸4 = 𝐽1𝑠2𝑝𝑥 + 𝐾1𝑠2𝑝𝑥 = 14,14𝑒𝑉 𝐸8 = 𝐽1𝑠2𝑝𝑧 + 𝐾1𝑠2𝑝𝑧 = 14,14𝑒𝑉
(1) (1) (1) (1) (1) (1)

𝐸3 = 𝐸5 = 𝐸7 𝐸4 = 𝐸6 = 𝐸8

𝐸𝐻𝑒 + 𝐽1𝑠2𝑝 = −54,82𝑒𝑉
(1)
𝐸𝐻𝑒 + 𝐸4 = −53,9eV
(1)
𝐸𝐻𝑒 + 𝐸2 = −55,4eV
(1)
𝐸𝐻𝑒 + 𝐸3 = −55,7eV
(1)
𝐸𝐻𝑒 + 𝐸1 = −57,8eV
𝐸𝐻𝑒 + 𝐽1𝑠2𝑠 = −56,61𝑒𝑉
The first excited levels of the helium atom.

𝐸𝐻𝑒 = −68,03,0𝑒𝑉
0 (0) (0)
𝜙1 = 𝑐1 𝜓1 − 𝜓2 = 2 1𝑠 1 2𝑠 2 − 2𝑠 1 1𝑠(2)
0 (0) (0)
𝜙2 = 𝑐1 𝜓1 + 𝜓2 = 2 1𝑠 1 2𝑠 2 + 2𝑠 1 1𝑠(2)
0 (0) (0)
𝜙3 = 𝑐3 𝜓3 − 𝜓4 = 2 1𝑠 1 2𝑝𝑥 2 − 1𝑠 2 2𝑝𝑥 (1)
0 (0) (0)
𝜙4 = 𝑐3 𝜓3 + 𝜓4 = 2 1𝑠 1 2𝑝𝑥 2 + 1𝑠 2 2𝑝𝑥 (1)
0 (0) (0)
𝜙5 = 𝑐5 𝜓5 − 𝜓6 = 2 1𝑠 1 2𝑝𝑦 2 − 1𝑠 2 2𝑝𝑦 (1)
0 (0) (0)
𝜙6 = 𝑐5 𝜓5 + 𝜓6 = 2 1𝑠 1 2𝑝𝑦 2 + 1𝑠 2 2𝑝𝑦 (1)
0 (0) (0)
𝜙7 = 𝑐7 𝜓7 − 𝜓8 = 2 1𝑠 1 2𝑝𝑧 2 − 1𝑠 2 2𝑝𝑧 (1)
0 (0) (0)
𝜙8 = 𝑐7 𝜓7 + 𝜓8 = 2 1𝑠 1 2𝑝𝑧 2 + 1𝑠 2 2𝑝𝑧 (1)


Perturbation Theory 2

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Perturbation Theory 2

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Perturbation Theory

Ana Claudia Monteiro Carvalho

Examples: Harmonic Oscillator, Potential

Perturbation Theory for a degenerate

Second major quantum-mechanical

We will study time-independente

Schrödinger equations for systems

Suppose also that the Hamiltonian 𝐻෡ is only slightly different from

෡ 0 𝜓𝑛0 = 𝐸𝑛0 𝜓𝑛0

We are able to solve. An example is the one-dimensional

We shall imagine that the perturbation is applied gradually, giving

perturbed wave function

We now expand 𝜓𝑛 and 𝐸𝑛 as Taylor series in powers of 𝜆

Considering the normalization condition for unperturbed

Equating the coefficients of the 𝜆0 terms, we have

Equating the coefficients of the 𝜆1 terms, we have

෡ 0 𝜓𝑛1 − 𝐸𝑛0 𝜓𝑛1 = 𝐸𝑛1 𝜓𝑛0 − 𝐻

all space, which gives:

Equating the coefficients of the 𝜆2 terms, we get

෡ 0 𝜓𝑛2 − 𝐸𝑛0 𝜓𝑛2 = 𝑬𝒏𝟐 𝝍𝒏𝟎 + 𝐸𝑛1 𝜓𝑛1 − 𝐻

The Second-Order Energy Correction.

The Second-Order Wavefunction Correction:

Taken from: Sakurai, Chap 5: Time-Independent Perturbation Theory, page 292

Examples: Harmonic Oscillator, Potential

Perturbation Theory for a degenerate

Figure: Sketches of the lowest-energy wavefunction (a) before

𝟏 𝑎 1Τ2 9 𝜋 1Τ2 9 𝑎 1Τ2 3𝑑 3𝑑ℏ2

෡0 |𝑛ۧ = 𝐸𝑛0 |𝑛ۧ = ℏ𝑤 𝑛 +

Second-Order Energy Correction

First-Order Energy Correction …

But we know that

Second-Order Energy Correction …

𝐿෠ 𝑧 |Λ2 , 𝑚ۧ = 𝑚𝑙 |Λ2 , 𝑚ۧ 𝐿෠2 |Λ2 , 𝑚ۧ = 𝑙(𝑙 + 1)|Λ2 , 𝑚ۧ

Considering the fundamental state for hydrogen atom

න𝑒 −𝑟Τ𝑎0 𝑟𝑐𝑜𝑠𝜃 𝑟𝑒 −𝑟Τ2𝑎0 𝑠𝑖𝑛𝜃𝑒 +𝑖𝜙 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙

න𝑟 2 𝑒 −3𝑟Τ2𝑎0 𝑐𝑜𝑠𝜃𝑠𝑖𝑛𝜃𝑒 +𝑖𝜙 𝑟 2 𝑠𝑖𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙

න𝑒 +𝑖𝜙 𝑑𝜙 න𝑐𝑜𝑠𝜃𝑠𝑖𝑛2 𝜃𝑑𝜃 න𝑟 4 𝑒 −3𝑟Τ2𝑎0 𝑑𝑟

2𝑝+1 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 0 2𝑝−1 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 0

න𝑒 −𝑟Τ𝑎0 𝑟𝑐𝑜𝑠𝜃 𝑟𝑒 −𝑟Τ2𝑎0 𝑐𝑜𝑠𝜃 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙

න𝑟 2 𝑒 −3𝑟Τ2𝑎0 𝑐𝑜𝑠 2 𝜃 𝑟 2 𝑠𝑒𝑛𝜃𝑑𝑟𝑑𝜃𝑑𝜙

න𝑑𝜙 න𝑐𝑜𝑠 2 𝜃𝑠𝑖𝑛𝜃𝑑𝜃 න𝑟 4 𝑒 −3𝑟Τ2𝑎0 𝑑𝑟

2𝑝0 𝑟𝑐𝑜𝑠𝜃 1𝑠 = 2,1,0 𝑟𝑐𝑜𝑠𝜃 1,0,0

2,1,0 𝑟𝑐𝑜𝑠𝜃 1,0,0 2 + 1,0,0 𝑟𝑐𝑜𝑠𝜃 2,1,0 2

Electronic hamiltonian operator for Helium atom

Taken from: Levine, I. N., Quantum Chemistry 4th Edition. Prentice

Perturbation Theory. Considering the first-

0 16𝑍 6 𝑒′2 2𝑍𝑟

Which, compared with the experimental value of – 79,0 eV, is in

Examples: Harmonic Oscillator, Potential

Perturbation Theory for a degenerate

where d indicates the degree of degeneracy.

perturbed wave function

Taken from: Levine, I. N., Quantum Chemistry Effect of a perturbation

Equating the coefficients of the 𝜆0 terms, we have

Equating the coefficients of the 𝜆1 terms, we have

෡ 0 𝜓𝑛1 − 𝑬𝒅𝟎 𝜓𝑛1 = 𝐸𝑛1 𝜙𝑛0 − 𝐻

This is a set of d linear, homogeneous equation in the d unknowns c’s

For nontrivial solutions, the determinant of the coefficients must vanish

As an example, consider the effect of a perturbation H’ on

Consider the perturbation as

211 𝐻 𝑽𝟎 න 𝒔𝒊𝒏 𝒙 𝒔𝒊𝒏 𝒙 𝒅𝒙

As a result of perturbation theory to the ground state of the

The lowest unperturbed excited states have n1 = 1, n2 =2 or

Taken from: Levine, I. N., Quantum Chemistry