Perturbation Theory/Appoximation methods for bound states

In quantum mechanics, the equation of motion can be solved exactly for very few problems like
particle in a box, linear harmonic oscillator , one electron atom , etc. For realistic applications we
need to learn the perturbation technique to find the changes in the energy level and wave function
in presence of an extra potential energy , which we may term as perturbing Hamiltonian. If the
perturbing Hamiltonian is independent of time, we can apply the stationary perturbation theory and
consider the time independent Schrodinger equation for the development. We have discussed in
lecture 1 that the stationary state the potential energy is independent of time, the bound states are
discrete and the probability density corresponding to the states is conserved i.e. stationary with
respect to time.

In the second part we will discuss time dependant perturbation theory wherein we will use time
dependent Schrodinger equation for dealing with the time dependent perturbing potential and
there we will calculate the transition probability between different states due to the perturbation

Stationary Perturbation theory for nondegenerate states

Here we will find the corrections to the energy level and the corresponding wave-function of a
discrete energy level due to a small time independent perturbing potential. Nondegenerate state
correspond to states wherein the eigenvalue has only one linearly independent eigen-function
example: levels in a one dimensional box, levels in linear harmonic Oscillator, ground state of
Hydrogen atom (𝜀𝜀1 , 𝜓𝜓100 ) etc. The degenerate state correspond to having more than one linearly
independent eigen-function for the given eigen-function, Example higher order states of Hydrogen
atom with quantum number n (≥2) are n2 fold degenerate.
(𝜀𝜀2 , 4𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝜓𝜓200 , 𝜓𝜓211 , 𝜓𝜓210 , 𝜓𝜓21−1 )

The Hamiltonian H can be written as

𝐻𝐻 = 𝐻𝐻0 + 𝐻𝐻′ … …(6.1)

Where 𝐻𝐻0 is simple such that its Schrodinger equation can be solved exactly and which satisfy a set
of eigenvalue equation

𝐻𝐻0 𝜓𝜓𝑛𝑛 = 𝜀𝜀𝑛𝑛 𝜓𝜓𝑛𝑛 …… (6.2)

Further 𝐻𝐻′ is small enough and regarded as the Perturbation over 𝐻𝐻0 .

Let the total Hamiltonian satisfy the eigenvalue Equation

𝐻𝐻𝐻𝐻 = 𝐸𝐸𝐸𝐸 …. (6.3)

As 𝐻𝐻′ is small, the eigenvalue 𝐸𝐸 and the eigenfunction𝛹𝛹 can be obtained as a power series in 𝐻𝐻′ .
For the purpose we introduce a parameter λ and we replace 𝐻𝐻 ′ by λ𝐻𝐻 ′ and express 𝐸𝐸 and 𝛹𝛹 in the
power series of λ𝐻𝐻′ i.e. λ. The two series are continuous and analyticfunction for all values of λ
between 0 and 1. The value zero for λ correspond to no perturbation and the value of one
correspond to the full strength perturbation. Hence different orders of perturbation correspond to
the coefficient of corresponding power of λ in the expansion.
We expand 𝛹𝛹 and E as:

𝛹𝛹 = 𝛹𝛹 (0) + λ𝛹𝛹 (1) + λ2 𝛹𝛹 (2) + ⋯

𝐸𝐸 = 𝐸𝐸 (0) + λ𝐸𝐸 (1) + λ2 𝐸𝐸 (2) + ⋯

Substituting these expansions in Eqn(6.3) and arranging them in powers of λ, we obtain

(𝐻𝐻0 + 𝜆𝜆𝐻𝐻′ )�𝛹𝛹 (0) + λ𝛹𝛹 (1) + λ2 𝛹𝛹 (2) + ⋯ �

= �𝐸𝐸 (0) + λ𝐸𝐸 (1) + λ2 𝐸𝐸 (2) + ⋯ ��𝛹𝛹 (0) + λ𝛹𝛹 (1) + λ2 𝛹𝛹 (2) + ⋯ �

Or

𝐻𝐻0 𝛹𝛹 (0) + 𝜆𝜆�𝐻𝐻0 𝛹𝛹 (1) + 𝐻𝐻′ 𝛹𝛹 (0) � + λ2 �𝐻𝐻0 𝛹𝛹 (2) + 𝐻𝐻′ 𝛹𝛹 (1) � + ⋯

= 𝐸𝐸 (0) 𝛹𝛹 (0) + 𝜆𝜆�𝐸𝐸 (0) 𝛹𝛹 (1) + 𝐸𝐸 (1) 𝛹𝛹 (0) � + λ2 �𝐸𝐸 (0) 𝛹𝛹 (2) + 𝐸𝐸 (1) 𝛹𝛹 (1) + 𝐸𝐸 (2) 𝛹𝛹 (0) � + ⋯

Comparing coefficients of different powers of λ on both sides we get:

𝐻𝐻0 𝛹𝛹 (0) = 𝐸𝐸 (0) 𝛹𝛹 (0) … (6.4. 𝑖𝑖)

𝐻𝐻0 𝛹𝛹 (1) + 𝐻𝐻′ 𝛹𝛹 (0) = 𝐸𝐸 (0) 𝛹𝛹 (1) + 𝐸𝐸 (1) 𝛹𝛹 (0) … …. … (6.4. 𝑖𝑖𝑖𝑖)

𝐻𝐻0 𝛹𝛹 (2) + 𝐻𝐻′ 𝛹𝛹 (1) = 𝐸𝐸 (0) 𝛹𝛹 (2) + 𝐸𝐸 (1) 𝛹𝛹 (1) + 𝐸𝐸 (2) 𝛹𝛹 (0) … .. … …. … (6.4. 𝑖𝑖𝑖𝑖𝑖𝑖)

The first equation ( 6.4.i) represent the eigen value equation of the unperturbed Hamiltonian 𝐻𝐻0 . At
the beginning in Eqn(6.2) we have defined the eigenvalue equation for 𝐻𝐻0 . So comparing equation
(6.4.i) with Eqn(6.2), we have

𝐸𝐸 (0) = 𝜀𝜀𝑛𝑛 𝑎𝑎𝑎𝑎𝑎𝑎 𝛹𝛹 (0) = 𝜓𝜓𝑛𝑛 … .. … (6.5)

Using eqn (6.5) , it is imperative that we find the energy correction to the nth eigenvalue 𝜀𝜀𝑛𝑛 and the
corresponding wave function 𝜓𝜓𝑛𝑛 due to the application of the perturbing potential.

First order correction :

As the wave-functions of the unperturbed Hamiltonian form acomplete orthonormal set, any wave
function like 𝛹𝛹 (1) and 𝛹𝛹 (2) can be expanded interms of the orthonormal functions as

(1) (2)
𝛹𝛹 (1) = � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ 𝑎𝑎𝑎𝑎𝑎𝑎 𝛹𝛹 (2) = � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ …. …. (6.6)
𝑘𝑘 𝑘𝑘

Substituting relations (6.5) and (6.6) in (6.4.ii) , we get

(1) (1)
𝐻𝐻0 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐸𝐸 (1) |𝜓𝜓𝑛𝑛 ⟩
𝑘𝑘 𝑘𝑘

(1) (1)
� 𝑎𝑎𝑘𝑘 𝐻𝐻0 |𝜓𝜓𝑘𝑘 ⟩ + 𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐸𝐸 (1) |𝜓𝜓𝑛𝑛 ⟩
𝑘𝑘 𝑘𝑘
 (1) (1)
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐸𝐸 (1) |𝜓𝜓𝑛𝑛 ⟩ … …. (6.7)
𝑘𝑘 𝑘𝑘

Multiplying Eqn (6.7) by 𝜓𝜓𝑛𝑛⋆ and integrating over space, we get

(1) (1)
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 ⟨𝜓𝜓𝑛𝑛 |𝜓𝜓𝑘𝑘 ⟩ + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 ⟨𝜓𝜓𝑛𝑛 |𝜓𝜓𝑘𝑘 ⟩ + 𝐸𝐸 (1) ⟨𝜓𝜓𝑛𝑛 |𝜓𝜓𝑛𝑛 ⟩
𝑘𝑘 𝑘𝑘

(1) (1)
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 𝛿𝛿𝑛𝑛𝑛𝑛 + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 𝛿𝛿𝑛𝑛𝑛𝑛 + 𝐸𝐸 (1) . 1
𝑘𝑘 𝑘𝑘

Eliminating the delta-function and summation, we obtain

(1) (1)
𝜀𝜀𝑛𝑛 𝑎𝑎𝑛𝑛 + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 𝑎𝑎𝑛𝑛 + 𝐸𝐸 (1)

𝐸𝐸 (1) = ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ … … (6.8)

So the first order correction to energy is the diagonal element 𝐻𝐻′ 𝑛𝑛𝑛𝑛 .
⋆
To find the first order correction to wave function, multiplying Eqn (6.7) by 𝜓𝜓𝑚𝑚 where 𝑚𝑚 ≠ 𝑛𝑛 and
integrate over space

(1) (1)
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐸𝐸 (1) |𝜓𝜓𝑛𝑛 ⟩
𝑘𝑘 𝑘𝑘

(1) (1)
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 ⟨𝜓𝜓𝑚𝑚 |𝜓𝜓𝑘𝑘 ⟩ + ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 ⟨𝜓𝜓𝑚𝑚 |𝜓𝜓𝑘𝑘 ⟩ + 𝐸𝐸 (1) ⟨𝜓𝜓𝑚𝑚 |𝜓𝜓𝑛𝑛 ⟩
𝑘𝑘 𝑘𝑘

(1) (1)
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 𝛿𝛿𝑚𝑚𝑚𝑚 + ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 𝛿𝛿𝑚𝑚𝑚𝑚 + 𝐸𝐸 (1) × 0
𝑘𝑘 𝑘𝑘

(1) (1)
𝜀𝜀𝑚𝑚 𝑎𝑎𝑚𝑚 + ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 𝑎𝑎𝑚𝑚

(1) (1)
⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ = 𝜀𝜀𝑛𝑛 𝑎𝑎𝑚𝑚 − 𝜀𝜀𝑚𝑚 𝑎𝑎𝑚𝑚

(1) ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩

𝑎𝑎𝑚𝑚 = 𝑓𝑓𝑓𝑓𝑓𝑓 𝑚𝑚 ≠ 𝑛𝑛 …… (6.9)
𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚

(1)
So in Eqn(6.6) , to determine the first order wave function 𝛹𝛹 (1) = ∑𝑚𝑚 𝑎𝑎𝑚𝑚 |𝜓𝜓𝑚𝑚 ⟩, we have obtained
(1)
all values of 𝑎𝑎𝑚𝑚 except the value 𝑘𝑘

(1)
𝑚𝑚 = 𝑛𝑛. To get the value of 𝑎𝑎𝑛𝑛 , we need to consider the normalization integral.

⟨𝜓𝜓𝑚𝑚 |𝐻𝐻 ′ |𝜓𝜓𝑛𝑛 ⟩

Upto first order wave function is 𝛹𝛹 = 𝛹𝛹 (0) + 𝛹𝛹 (1) = |𝜓𝜓𝑛𝑛 ⟩ + ∑′𝑚𝑚 |𝜓𝜓𝑚𝑚 ⟩ + 𝑎𝑎𝑛𝑛(1) |𝜓𝜓𝑛𝑛 ⟩
𝜀𝜀𝑛𝑛 −𝜀𝜀𝑚𝑚

The prime over the summation indicate that the summation does not include the term m = n.
The normalization integral ⟨𝛹𝛹|𝛹𝛹⟩ = 1

(1)∗ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩∗

′ ′ ⟨𝜓𝜓 |𝐻𝐻 ′ |𝜓𝜓 ⟩
𝑚𝑚 𝑛𝑛
�(1 + 𝜆𝜆𝑎𝑎𝑛𝑛 )⟨𝜓𝜓𝑛𝑛 ⌋ + 𝜆𝜆 � ⟨𝜓𝜓𝑚𝑚 ⌋� �(1 + 𝜆𝜆𝜆𝜆𝑛𝑛(1) )|𝜓𝜓𝑛𝑛 ⟩ + 𝜆𝜆 � |𝜓𝜓𝑚𝑚 ⟩� = 1
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚 𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚

(1)∗ (1)
�1 + 𝜆𝜆𝑎𝑎𝑛𝑛 � �1 + 𝜆𝜆𝜆𝜆𝑛𝑛 � ⟨𝜓𝜓𝑛𝑛 ⌋|𝜓𝜓𝑛𝑛 ⟩ + 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑜𝑜𝑜𝑜 λ2 = 1

Up to first order in 𝜆𝜆, the eqn reduces to

(1)∗ (1)
𝑎𝑎𝑛𝑛 + 𝑎𝑎𝑛𝑛 = 0
(1) (1)
Hence real par of 𝑎𝑎𝑛𝑛 = 0 . Hence we can consider 𝑎𝑎𝑛𝑛 = 0

⟨𝜓𝜓𝑚𝑚 |𝐻𝐻 ′ |𝜓𝜓𝑛𝑛 ⟩

Hence wave function up to first order is 𝛹𝛹 = 𝛹𝛹 (0) + 𝛹𝛹 (1) = |𝜓𝜓𝑛𝑛 ⟩ + ∑′𝑚𝑚 |𝜓𝜓𝑚𝑚 ⟩ ….(6.10)
𝜀𝜀𝑛𝑛 −𝜀𝜀𝑚𝑚

Second order correction to energy

Considering the second order equation as given in Eqn(6.4.iii) and substituting values obtained for
𝐸𝐸 (0) , 𝛹𝛹 (0) , 𝐸𝐸 (1) 𝑎𝑎𝑛𝑛𝑛𝑛 𝛹𝛹 (1) , from eqns (6.5),(6.8) and (6.10) and 𝛹𝛹 (2) from eqn(6.6) , we get

𝐻𝐻0 𝛹𝛹 (2) + 𝐻𝐻′ 𝛹𝛹 (1) = 𝐸𝐸 (0) 𝛹𝛹 (2) + 𝐸𝐸 (1) 𝛹𝛹 (1) + 𝐸𝐸 (2) 𝛹𝛹 (0)

(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
𝐻𝐻0 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐻𝐻′ � |𝜓𝜓𝑚𝑚 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘
(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
= 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ � |𝜓𝜓𝑚𝑚 ⟩ + 𝐸𝐸 (2) |𝜓𝜓𝑛𝑛 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘

(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
� 𝑎𝑎𝑘𝑘 𝐻𝐻0 |𝜓𝜓𝑘𝑘 ⟩ + 𝐻𝐻′ � |𝜓𝜓𝑚𝑚 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘
(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
= 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ � |𝜓𝜓𝑚𝑚 ⟩ + 𝐸𝐸 (2) |𝜓𝜓𝑛𝑛 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘

(2) ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩

′
′
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + 𝐻𝐻 � |𝜓𝜓𝑚𝑚 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘
(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
= 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 |𝜓𝜓𝑘𝑘 ⟩ + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ � |𝜓𝜓𝑚𝑚 ⟩ + 𝐸𝐸 (2) |𝜓𝜓𝑛𝑛 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘

Multiplying the above by 𝜓𝜓𝑛𝑛⋆ and integrating over space, we get

(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 ⟨𝜓𝜓𝑛𝑛 |𝜓𝜓𝑘𝑘 ⟩ + � ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑚𝑚 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘
(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
= 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 ⟨𝜓𝜓𝑛𝑛 |𝜓𝜓𝑘𝑘 ⟩ + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ � ⟨𝜓𝜓𝑛𝑛 |𝜓𝜓𝑚𝑚 ⟩ + 𝐸𝐸 (2) ⟨𝜓𝜓𝑛𝑛 |𝜓𝜓𝑛𝑛 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘
 (2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
� 𝑎𝑎𝑘𝑘 𝜀𝜀𝑘𝑘 𝛿𝛿𝑛𝑛𝑛𝑛 + � ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑚𝑚 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘
(2)
′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
= 𝜀𝜀𝑛𝑛 � 𝑎𝑎𝑘𝑘 𝛿𝛿𝑛𝑛𝑛𝑛 + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ � × 𝛿𝛿𝑛𝑛𝑛𝑛 + 𝐸𝐸 (2) × 1
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚
𝑘𝑘

In rhs the second term the summation do not contain the term m = n. as such all terms in the sum is
zero.

(2)
′ ⌊⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩⌋2 (2)
𝜀𝜀𝑛𝑛 𝑎𝑎𝑛𝑛 + � = 𝜀𝜀𝑛𝑛 𝑎𝑎𝑛𝑛 + 𝐸𝐸 (2)
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚

′ ⌊⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩⌋2

𝐸𝐸 (2) = � …. …… (6.11)
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚

Hence energy considered up to second order correction is

′ ⌊⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩⌋2

𝐸𝐸 = 𝜀𝜀𝑛𝑛 + ⟨𝜓𝜓𝑛𝑛 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩ + �
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚

The wavefunction considered up to first order correction is

′ ⟨𝜓𝜓𝑚𝑚 |𝐻𝐻′ |𝜓𝜓𝑛𝑛 ⟩
𝛹𝛹 = |𝜓𝜓𝑛𝑛 ⟩ + � |𝜓𝜓𝑚𝑚 ⟩
𝑚𝑚 𝜀𝜀𝑛𝑛 − 𝜀𝜀𝑚𝑚

In the next lecture we will discuss the applications of this theory