Quantum Mechanics 2 (PHY 4423) Lecture 2 (Jan 23)

Spring 2023

José A. Morales E., UTSA Math and Physics & A. Depts.

Abstract
TIME-INDEPENDENT PERTURBATION THEORY: (a) calculate first-order
corrections to non-degenerate energy levels and to corresponding wave func-
tions. (b) obtain second-order corrections to non-degenerate energy levels; (c)
find first-order corrections to degenerate energy levels and to corresponding
zero-order “good” wave functions; (d) non-degenerate Time-Independent Per-
turbation Theory as an Iterative Method.

1. Time-Independent Perturbation Theory:

In shorthand, time-independent perturbation theory lets us, having previ-

ously solved the Eigen-problem of Schroedinger equation for a given Hamiltonian
(knowing then its stationary states), to find increasingly more accurate eigenval-
ues and eigenfunctions for a new problem where we add a (small) perturbation
term to the previously solved Hamiltonian. This is obtained by performing a
matching power series expansion (where the expansion parameter controls the
magnitude of the perturbation in the Hamiltonian) for the new eigenvalues and
eigenfunctions, identifying their first order corrections, second order, etc. At
some point in the matching it is relevant in the equations if the energy eigen-
values are degenerate or not. Because usually we care for a perturbation of a
given magnitude rather than the whole family of perturbations given by differ-
ent magnitudes of the expansion parameter, at the end we take the value of
this parameter as one. The approach abovementioned is time-independent in
the sense that is restricted to the spatial part of Schroedinger equation, as it
simply lets us obtain subsequent corrections to the eigen-problem for the new
Hamiltonian and its related stationary states.

1.1. First-order corrections to nondegenerate energy levels & wave functions

So we know the (non-degenerate) eigensolutions to the Schroedinger equation
for a given Hamiltonian H 0 , that is

Email address: jose.morales4@utsa.edu (José A. Morales E., UTSA Math and Physics
& A. Depts.)

Preprint submitted to Blackboard (TBS) January 23, 2023

1.1 First-order corrections to nondegenerate energy levels & wave functions 2

H 0 ψn0 = En0 ψn0

where by non-degenerate we mean that two linearly independent eigenfunc-
tions cannot have the same energy eigenvalue. We also know that {ψn0 } is a
complete set, so any function in the Hilbert space can be expressed in terms of
this orthonormal basis. Now our goal is, for a new Hamiltonian made of the
previous one plus a perturbation in the potential,

H = H 0 + λH 0
(where λ is an expansion parameter that controls the size of the perturba-
tion) to find its eigenfunctions and eigenvalues:

Hψn = En ψn
Because the change in the eigen-set is related to the perturbation, we will
write the new eigenvalues and eigenfunctions as a power series in λ:
X
ψn = λj ψnj = ψn0 + λψn1 + λ2 ψn2 + ...
j=0

X
En = λj Enj = En0 + λEn1 + λ2 En2 + ...
j=0

Notice a couple things. First, a perturbative expansion relies on the assump-

tion of a small perturbation (meaning the expansion is valid for small values of
λ). Second, when λ = 0, there’s no perturbation, and we return to the old eigen-
sets. It is when λ 6= 0 that you start getting corrections to the eigen-solutions,
and in this lecture we’ll focus only on the first order and second order correc-
tions, where we’ll call En1 the first-order correction to the n-th eigenvalue, ψn1 is
called the first-order correction to the n-th eigenfunction, En2 and ψn2 are called
the second-order corrections, etc. Now that we have expressed the new eigenset
as a power series expansion, we substitute these expressions in the Eigenvalue
Problem for the new Hamiltonian:

X
(H 0 + λH 0 ){ψn0 + λψn1 + λ2 ψn2 + ...} = (H 0 + λH 0 ){ λj ψnj } = Hψn = En ψn =
j=0

X X
=( λk Enk )( λj ψnj ) = (En0 + λEn1 + λ2 En2 + ...)(ψn0 + λψn1 + λ2 ψn2 + ...)
k=0 j=0

Since we have two equal power series in λ we’ll equate terms of the same
degree in λ, and we’ll obtain different equalities for given orders in λ. So we
have
1.1 First-order corrections to nondegenerate energy levels & wave functions 3

X X X
H 0 ψn0 + λj (H 0 ψnj + H 0 ψnj−1 ) = { λj H 0 ψnj } + H 0 { λj ψnj−1 } =
j=1 j=0 j=1

X X X j
X X j
X
=( λk Enk )( λj ψnj ) = λj Enk ψnj−k = En0 ψn0 + λj Enk ψnj−k
k=0 j=0 j=0 k=0 j=1 k=0

so now we obtain an equation to zero order λ0 in λ

H 0 ψn0 = En0 ψn0

which is simply the eigen-solution to the old Hamiltonian (indicating the
solution when there’s no perturbation for λ = 0 and being simply a good sanity
check of the solving method for consistency rather than providing new informa-
tion), another equation to first order λ1 in λ:
1
X
H 0 ψn1 + H 0 ψn0 = Enk ψn1−k = En0 ψn1 + En1 ψn0
k=0

and then the equation related to second order λ2 in λ:

2
X
H 0 ψn2 + H 0 ψn1 = Enk ψn2−k = En0 ψn2 + En1 ψn1 + En2 ψn0
k=0

We could keep doing the same for higher λk , k > 2 orders, but we’ll stop
at second order for the purpose of this lecture. It is to be stated that we care
for a perturbation with value λ = 1, so ultimately that is the value at which
we’ll fix it.
We’ll focus now on the first-order equation, in particular in its corrections
to non-degenerate energy levels and wave functions.

H 0 ψn1 + H 0 ψn0 = En0 ψn1 + En1 ψn0

We’ll obtain the first-order corrections to the n-th energy eigenvalue by tak-
ing the inner product with respect to ψn0 , so we have

En0 ψn0 |ψn1 + ψn0 |H 0 ψn0 = H 0 ψn0 |ψn1 + ψn0 |H 0 ψn0 = ψn0 |H 0 ψn1 + H 0 ψn0 =

= ψn0 |En0 ψn1 + En1 ψn0 = En0 ψn0 |ψn1 + En1

so comparing terms we have that the new information provided by first order
perturbation theory is the following:

ψn0 |H 0 |ψn0 = En1

1.1 First-order corrections to nondegenerate energy levels & wave functions 4

namely, “the first-order correction to the energy is the expectation value of

the perturbation in the Hamiltonian for the unperturbed state”.
Now we want to know the first order correction to the wave function. For
that, we separate terms according to their wave-function

(H 0 − En0 )ψn1 = −(H 0 − En1 )ψn0

Since we know all terms above except for ψn1 the above is an inhomogeneous
differential equation for ψn1 . Most importantly, {ψn0 } is a complete set, so it can
express any function in the Hilbert space, in particular ψn1 . Therefore, we have
X
ψn1 = c(n)
m ψm
0

m6=n

where we omit m = n so that in ψn = ψn0 + λψn1 + λ2 ψn2 + ..., thinking of it

as an expression of ψn in terms of orthogonal functions instead of as a power
expansion in λ (taking λ = 1 for example), the subsequent term ψn1 has no
component in terms of ψn0 (if it had one, it could be combined with the previous
term ψn0 for the expression of ψn and therefore removed from ψn1 ; this would
be equivalent to the first steps in a Gram-Schmidt orthogonalization process).
(n)
We’ll solve our diff. eq. for ψn1 by finding the coefficients cm . Plugging in its
expression in terms of the complete set (related to the old eigen-problem) in our
inhomogeneous diff. eq., then

X X
0
c(n) 0 0 0 0 0
m (Em − En )ψm = (H − En ) c(n) 0 1 0
m ψm = −(H − En )ψn
m6=n m6=n

Since we have a complete set, we’ll take the inner product with respect to a
given ψl0

* +
X X
c(n) 0 0
m (Em −En )δlm = ψl0 | c(n) 0
m (Em − En0 )ψm
0
= − ψl0 |H 0 |ψn0 +En1 ψl0 |ψn0
m6=n m6=n

For l = n the left hand side is zero and together with the right hand side we
have a restatement of the first-order correction to the energy we found before.
For the case l 6= n, since we assumed a non-degenerate unperturbed energy
spectrum, that means that different elements in the complete set cannot corre-
spond to the same energy eigenvalue, and therefore El0 − En0 6= 0 if l 6= n, so we
have
(n)
cl (El0 − En0 ) = − ψl0 |H 0 |ψn0
therefore for m 6= n it holds that
0
ψm |H 0 |ψn0
c(n)
m =
En0 − Em 0
1.1 First-order corrections to nondegenerate energy levels & wave functions 5

and finally we get the first-order correction for the wave function in terms
of the complete set of the unperturbed eigen-problem as below:
0
X ψm |H 0 |ψn0 0
ψn1 = 0 0
ψm
En − Em
m6=n

for the case of non-degenerate energy levels for the unperturbed problem.
The last two equations also point out why it was important to express ψn1
without ψn0 component in our treatment.

1.1.1. Example of applications of first-order nondegenerate perturbation theory

1. Consider the physical situation of an anharmonic oscillator with Hamilto-
nian
p2 mω 2 x2 x2
H= + (1 + 2 ) = H 0 + H 0
2m 2 b
where the unperturbed Hamiltonian is harmonic
p2 mω 2 x2
H0 = +
2m 2
and the anharmonic perturbation is
1 mω 2 4
H0 = x
2 b2
(a) Find the first-order correction to the energy by perturbation theory.
1 mω 2 0 4 0
En1 = ψn0 |H 0 |ψn0 = ψn |x |ψn
2 b2
with ψn0 the n−th harmonic oscillator state function,
cn † n 0
ψn0 = (a ) ψ0
c0
where the cn ’s are introduced for normalization. At the same time,
we can express the position operator in terms of ladder operators:
r
~
x= (a + a† ) =⇒
2mω
2 2
~ 2 ~ 2 X j † 2−j X q † 2−q
x4 = ( ) ((a + a† )2 )2 = ( ) ( a (a ) )( a (a ) )
2mω 2mω j=0 q=0

but when we take the inner product ψn0 |x4 |ψn0 only the terms of
|x4 ψn0 that are proportional to ψn0 will survive, meaning terms from
the x4 operator generated by aq (a† )4−q so that the raising and low-
ering renders us back to a state proportional to ψn0 . So
−4≤q,p,i,j≤4
~ 2 X
x4 = ( ) ( aq ap ai aj ) + noncontributing terms
2mω q+p+i+j=0
1.1 First-order corrections to nondegenerate energy levels & wave functions 6

where (in this temporary notation) we allow negative indices to rep-

resent powers of the raising operator, i.e., a− = a† , so
~ 2 2 †2
x4 = ( ) (a a +aa† aa† +aa†2 a+a† a2 a† +a† aa† a+a†2 a2 )+noncontributing terms
2mω
We’ll use the property a = ∂a† in the raising operator representa-
tion, in which the effect of operating with a is equivalent to take a
derivative with respect to a† . This is because
r r
mω p mω
a= (x + iy), y = , a† = (x − iy),
2~ mω 2~
and it can be proved by Complex Analysis that an analytic function
(therefore satisfying Cauchy-Riemann) has a derivative operator
∂x+iy [∂x <{} + i∂x ={}] 1
∂a = p mω = p mω = p mω [∂y = − i∂y <{}] =
2~ 2~ 2~

1 {∂x − i∂y } ∂ − i∂
= p mω [{∂x −i∂y }<{}+i{∂x −i∂y }=] = p mω [<{}+i=] = xp mωy
2 2~ 2 2~ 2 2~
and also
∂x−iy [∂x <{} + i∂x ={}] −1
∂a† = p mω = p mω = p mω [∂y = − i∂y <{}] =
2~ 2~ 2~

1 {∂x + i∂y } ∂x + i∂y

= p mω [{∂x +i∂y }<{}+i{∂x +i∂y }=] = [<{}+i=] = q
2 mω
p
2 2~ 2~
2mω
~
p mω ~∂x
but p = −i~∂x and x = i~∂p , therefore a = 2~ (i~∂p + mω ) =
q
~
2mω (i∂y + ∂x ) = ∂a† . So we have

~ 2 0 2 †2
ψn0 |x4 |ψn0 = ( ) ψn |a a + aa† aa† + aa†2 a + a† a2 a† + a† aa† a + a†2 a2 |ψn0 =
2mω
 
~ 2 0 2 †2 † † †2 † 2 † † † †2 2 cn † n 0
( ) ψn |∂ a† a + ∂a† a ∂a† a + ∂a† a ∂a† + a ∂a† a + a ∂a† a ∂a† + a ∂a† | (a ) ψ0 =
2mω c0
~ 2
( ) ((n+2)(n+1)+(n+1)2 +n(n+1)+(n+1)n+n2 +n(n−1)) ψn0 |ψn0 =
2mω
~ 2 ~ 2
( ) ((3 + 4n)(n + 1) + n(2n − 1)) = ( ) 3(1 + 2n(n + 1))
2mω 2mω
Therefore
3 mω 2 ~ 2 3 ~2
En1 = 2
( ) (1 + 2n(n + 1)) = (1 + 2n(n + 1))
2 b 2mω 8 b2 m
and the energy eigenvalues, up to first-order, are
1 3 mω 2 ~ 2 1 3 ~
En ≈ En0 +En1 = (n+ )~ω+ ( ) (1+2n(n+1)) = ~ω[n+ + 2 (1+2n(n+1))]
2 2 b2 2mω 2 8 b ωm
REFERENCES 7

(b) Identify the change in frequency introduced by the anharmonic per-

turbation added above, and the anharmonic oscillation introduced by
examining the energy levels: Rewriting our first-order result in (a)
as
1 3 ~ 1 1
En ≈ ~ω[n + + (n + + n2 )] = (n + )~(ω + δω) + n2 ~δω
2 4 b2 ωm 2 2
with
3~
δω =
4mb2
we notice that the anharmonic perturbation increases the frequency
by δω, and it makes the spacing between levels increase with increas-
ing energy due to n2 ~δω. The term n2 ~δω identifies the oscillations
as anharmonic.

References

[1] Introduction to Quantum Mechanics, 3rd Edition, by D.J. Griffiths and D.

L. Schroeter (2018, Cambridge University Press).
[2] Quantum Mechanics, by David McIntyre (Pearson, 2012).
[3] Introduction to Perturbation Methods, by M. H. Holmes, Texts in Applied
Mathematics 20, Springer, 1995.
[4] Elementary Quantum Mechanics, by D. Saxon, Holden-Day, 1968.
[5] Mecánica Cuántica (Lecture Notes), Luis Fernando Magaña, FC-UNAM,
Mexico 2006.