Module 4 : Applications of Quantum

Mechanics
(Lecture Notes for Engineering Physics : BAPHY105)

Vishnudath K N
Assistant Professor
Department of Physics, School of Advanced Sciences
VIT Vellore
2

Disclaimer
These lecture notes do not claim originality. They are an assimilation of existing materials
from various standard textbooks and lecture notes, compiled and reorganized to suit the
structure and requirements of the course syllabus.

Note
These lecture notes are continuously updated based on classroom discussions and ques-
tions asked by students. There may still be mistakes, and if you find any, please feel free
to write to me at [Link]@[Link].
Contents

4 Applications of Quantum Mechanics 4

4.1 The Infinite Square Well . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.1.1 The Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.1.2 Time-Independent Schrödinger Equation . . . . . . . . . . . . . . 5
4.1.3 Boundary Conditions . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1.4 Energy Eigenvalues . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.1.5 Normalized Wavefunctions . . . . . . . . . . . . . . . . . . . . . . 6
4.1.6 Properties of Eigenfunctions . . . . . . . . . . . . . . . . . . . . . 6
4.1.7 Stationary States . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2 Extension to the Three-Dimensional Case . . . . . . . . . . . . . . . . . . 12
4.2.1 The Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2.2 Separation of Variables . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2.3 Boundary Conditions and Solutions . . . . . . . . . . . . . . . . . 12
4.2.4 Wavefunctions and Energies . . . . . . . . . . . . . . . . . . . . . 13
4.2.5 Degeneracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.3 Quantum Tunneling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

3
Module 4

Applications of Quantum Mechanics

Introduction
In the previous module we introduced the fundamental postulatess of quantum mechanics,
including the Schrödinger equation, operators, and the probabilistic interpretation of the
wavefunction. In this chapter we apply those principles to a number of important physical
systems. These examples illustrate how quantum mechanics predicts phenomena that
have no classical counterpart.
We begin with the infinite square well, one of the simplest and most important
exactly solvable models in quantum mechanics. Despite its simplicity, this system clearly
demonstrates several fundamental quantum features such as the quantization of energy,
the existence of stationary states, and the role of boundary conditions in determining the
allowed wavefunctions.
We then extend the discussion to the three-dimensional infinite potential well,
where the method of separation of variables allows us to construct solutions from the
one-dimensional case. This example also introduces the concept of degeneracy, where
different quantum states can share the same energy.
Finally, we discuss quantum tunnelling, a purely quantum-mechanical phenomenon
in which a particle can penetrate and pass through a potential barrier even when its energy
is less than the barrier height. Tunnelling plays an important role in many physical
processes and technological applications, including α-decay in nuclear physics and the
operation of devices such as the scanning tunnelling microscope (STM).
Through these examples, we see how the abstract formalism of quantum mechanics
leads to concrete and experimentally observable predictions.

4.1 The Infinite Square Well

4.1.1 The Potential
The infinite square well is defined as
(
0, 0 ≤ x ≤ a,
V (x) = (4.1)
∞, otherwise.

A particle is thus confined within the region [0, a] and cannot exist outside. See Fig. 4.1.

4
4.1. THE INFINITE SQUARE WELL 5

Figure 4.1: The infinite square well of width a. (Adapted from Introduction to Quantum
Mechanics by David J. Griffiths and Darelle F. Schroeter, 3rd edition, for instructional
use only.)

4.1.2 Time-Independent Schrödinger Equation

Inside the well (0 < x < a), the potential is zero, so the time-independent Schrödinger
equation reads
ℏ2 d2 ψ
− = Eψ.
2m dx2
Rearranging, √
d2 ψ 2mE
2
= −k 2 ψ, k≡ .
dx ℏ
This is the simple harmonic oscillator equation, whose general solution is
ψ(x) = A sin(kx) + B cos(kx).

4.1.3 Boundary Conditions

Since the wavefunction must vanish where V (x) = ∞:
ψ(0) = 0, ψ(a) = 0.
At x = 0, we find ψ(0) = B = 0. Hence
ψ(x) = A sin(kx).
At x = a, the condition ψ(a) = 0 requires
A sin(ka) = 0.
For a nontrivial solution (A ̸= 0), this implies
ka = nπ, n = 1, 2, 3, . . .
so1
nπ
kn = .
a
1
The case n = 0 corresponds to k = 0, which would give ψ(x) = 0 everywhere, the trivial non-physical
solution. Negative n values lead to sin(−nπx/a) = − sin(nπx/a), which differ only by an overall sign
and hence do not represent new physical states.
6 MODULE 4. APPLICATIONS OF QUANTUM MECHANICS

4.1.4 Energy Eigenvalues

The corresponding energies are
ℏ2 kn2 n2 π 2 ℏ2
En = = , n = 1, 2, 3, . . .
2m 2ma2
Thus the spectrum is discrete and quadratic in n.

4.1.5 Normalized Wavefunctions

Normalization requires Z a
|ψ(x)|2 dx = 1.
0
Substituting ψ(x) = A sin(nπx/a),
Z a  nπx 
2 2
|A| sin dx = 1.
0 a
Ra
sin2 nπx
dx = a2 , we find


Using 0 a
r
a 2
|A|2 = 1 ⇒ A= .
2 a
Hence the normalized eigenfunctions are
r
2  nπx 
ψn (x) = sin , n = 1, 2, 3, . . .
a a
The lowest state, ψ1 (x), is called the ground state, with energy

π 2 ℏ2
E1 = .
2ma2
The next state, ψ2 (x), is the first excited state, with energy

4π 2 ℏ2
E2 = ,
2ma2
and ψ3 (x) is the second excited state, with energy

9π 2 ℏ2
E3 = .
2ma2
In general, the nth eigenfunction corresponds to the (n − 1)th excited state.
The first three normalized wavefunctions ψ1 (x), ψ2 (x), ψ3 (x) are illustrated in Fig. 4.2,
which shows their sinusoidal form within the infinite square well.

4.1.6 Properties of Eigenfunctions

The normalized eigenfunctions of the infinite square well are
r
2  nπx 
ψn (x) = sin , n = 1, 2, 3, . . .
a a
4.1. THE INFINITE SQUARE WELL 7

Figure 4.2: The first three stationary states ψ1 (x), ψ2 (x), and ψ3 (x) for the infinite square
well of width a. (Adapted from Introduction to Quantum Mechanics by David J. Griffiths
and Darelle F. Schroeter, 3rd edition, for instructional use only.)

Proof of Orthonormality
Consider the inner product of two eigenfunctions:
Z a
2 a  mπx   nπx 
Z
Imn = ψm (x) ψn (x) dx = sin sin dx.
0 a 0 a a
Using the trigonometric identity

sin α sin β = 21 [cos(α − β) − cos(α + β)] ,

we obtain ( )
a   
(m − n)πx
Z
1 (m + n)πx
Imn = cos − cos dx.
a 0 a a
Evaluating the integrals:
Z a    a
(m ± n)πx a (m ± n)πx
cos dx = sin .
0 a (m ± n)π a 0

At the limits, sin[(m ± n)π] = 0, so both terms vanish whenever m ̸= n. Thus,

Imn = 0 for m ̸= n.

For m = n, we have
Z a
2 2
 nπx  2 a
Inn = sin dx = · = 1.
a 0 a a 2
Hence, Z a
ψm (x)ψn (x) dx = δmn ,
0
showing that the eigenfunctions form an orthonormal set.

Completeness and Probabilistic Interpretation

The eigenfunctions also form a complete basis. Any square-integrable wavefunction f (x)
defined on [0, a] can be expanded as
∞
X Z a
f (x) = cn ψn (x), cn = ψn (x)f (x) dx.
n=1 0
8 MODULE 4. APPLICATIONS OF QUANTUM MECHANICS

The coefficients cn carry physical meaning:

|cn |2
is the probability of finding the particle in the stationary state ψn (x) with corresponding
energy En .

4.1.7 Stationary States

The full time-dependent solutions (stationary states) are
r
2  nπx  −i n2 π22ℏ t
Ψn (x, t) = ψn (x)e−iEn t/ℏ = sin e 2ma .
a a

Summary
• The infinite square well confines the particle to 0 ≤ x ≤ a.
• Solutions inside the well are sinusoidal, vanishing at the boundaries.
• Allowed energies are quantized: En ∝ n2 .
• Normalized eigenfunctions are standing waves of the form sin(nπx/a).
• The eigenfunctions are orthonormal and complete, forming a basis for expansions
of arbitrary wavefunctions in the well.

Problems: One-Dimensional Infinite Square Well

Problem 1 The initial wavefunction at time t = 0 for a particle in a one-dimensional
potential well of width a is given as,
(
A x(a − x), 0 ≤ x ≤ a,
Ψ(x, 0) =
0, otherwise.
P
(a) Find A by normalization. (b) Find the expansion coefficients cn in Ψ(x, 0) = n cn ψn (x)
where ψn correspond to the stationary states. (c) State which cn vanish and give the closed
form of the nonzero ones.
Solution. (a) Normalize:
Z a r
5
2 2 2 2a 30
1 = |A| x (a − x) dx = |A| =⇒ A = .
0 30 a5
(b) The coefficients are
Z a r Z a
2  nπx 
cn = ψn (x) Ψ(x, 0) dx = A x(a − x) sin dx.
0 a 0 a
Carrying out the integral (integration by parts twice or using standard integrals) one
finds (after simplification) (please verify!!)
√
8 15
cn = for n odd, cn = 0 for n even.
(nπ)3
4.1. THE INFINITE SQUARE WELL 9
√
8 15
(c) Thus only odd n appear; e.g. c1 = , and the probability to measure E1 is
π3
|c1 |2 ≈ 0.9986 (the majority of the weight is in the ground state for this particular f (x)).
The time evolution follows immediately:
X
Ψ(x, t) = cn ψn (x) e−iEn t/ℏ .
n odd

Problem 2 In the above problem, find the expectation values of position, energy
and momentum of the particle at t = 0. Also, find the unceratinties in position and
momentum. Verify the uncertainty relation.

Hints:
Given (
A x(a − x), 0 ≤ x ≤ a,
Ψ(x, 0) =
0, otherwise
Normalization gives r
30
A=
a5
For the given wave function that is non–zero only in the interval 0 ≤ x ≤ a, the
expectation value of any operator Ô is (at t = 0),
Z a
⟨Ô⟩ = Ψ∗ (x, 0) Ô Ψ(x, 0) dx
0

Expectation value of position

Z a
⟨x⟩ = Ψ∗ (x, 0) x Ψ(x, 0) dx
0

Expectation value of momentum

Z a  
∗ ∂
⟨px ⟩ = Ψ (x, 0) −iℏ Ψ(x, 0) dx
0 ∂x

Expectation value of energy

⟨E⟩ = ⟨H⟩ and use ĤΨn = En Ψn

to evaluate Z a
⟨H⟩ = Ψ∗ (x, 0)ĤΨ(x, 0) dx
0

To compute the uncertainties, first calculate

Z a
2
⟨x ⟩ = Ψ∗ (x, 0) x2 Ψ(x, 0) dx
0
Z a  2

∗ 2 ∂
⟨p2x ⟩ = Ψ (x, 0) −ℏ Ψ(x, 0) dx
0 ∂x2
10 MODULE 4. APPLICATIONS OF QUANTUM MECHANICS

Uncertainty in position
p
σx = ⟨x2 ⟩ − ⟨x⟩2

Uncertainty in momentum
p
σpx = ⟨p2x ⟩ − ⟨px ⟩2

Finally verify the Heisenberg uncertainty relation

ℏ
σx σpx ≥
2

Problem 3 Consider a particle in a one-dimensional box of width a. It is given that

at t = 0 the particle is equally likely to be anywhere in the left half:
(
A, 0 ≤ x ≤ a/2,
Ψ(x, 0) =
0, a/2 < x ≤ a.
P
(a) Find A. (b) Find the expansion coefficients cn in Ψ(x, 0) = n cn ψn (x) where ψn
correspond to the stationary states. (c) What is the probability to measure the ground-
state energy E1 ?
Solution. (a) Normalization:
Z a/2 r
a 2
1 = |A|2 dx = |A|2 =⇒ A = .
0 2 a
(b) Coefficients
Z a
r Z a/2
2  nπx 
cn = ψn (x)Ψ(x, 0) dx = A sin dx.
0 a 0 a
p
With A = 2/a the prefactor becomes 2/a, so
Z a/2
2  nπx  2 a  nπ  2  nπ 
cn = sin dx = · 1 − cos = 1 − cos .
a 0 a a nπ 2 nπ 2
This compact form shows the selection structure; evaluating the first few:
2 2 2 2
c1 = , c2 = , c3 = , c4 = 0, c5 = , ...
π π 3π 5π
(c) Probability to measure E1 :
 2 2 4
P (E1 ) = |c1 |2 = = ≈ 0.4053.
π π2
−iEn t/ℏ
P
The full time evolution is Ψ(x, t) = n cn ψn (x)e .

Remarks.
Ra
• In any expansion Ψ(x, 0) = n cn ψn (x), the coefficient cn is given by cn = 0 ψn∗ (x)Ψ(x, 0) dx,
P
and |cn |2 is the probability that an energy measurement yields En .
4.1. THE INFINITE SQUARE WELL 11

Problem 4
A particle is confined in a one–dimensional infinite potential well of width L. The
energy levels of the particle are given by

n2 π 2 ℏ2
En = , n = 1, 2, 3, . . .
2mL2
Suppose the particle makes a transition from the state n = 3 to the state n = 2 by
emitting a photon.

(a) Find the energy of the emitted photon.

(b) Determine the wavelength of the emitted photon.

Solution
The energy of the emitted photon equals the difference between the initial and final
energy levels:

Eγ = Ei − Ef
For the transition n = 3 → n = 2,

9π 2 ℏ2 4π 2 ℏ2
E3 = , E2 =
2mL2 2mL2
Therefore,

Eγ = E3 − E2

9π 2 ℏ2 4π 2 ℏ2
Eγ = −
2mL2 2mL2
5π 2 ℏ2
Eγ =
2mL2
The energy of a photon is related to its wavelength by
hc
Eγ =
λ
Thus,
hc
λ=
Eγ
Substituting the expression for Eγ ,
hc
λ= 5π 2 ℏ2
2mL2

2mL2 hc
λ=
5π 2 ℏ2
h
Using ℏ = 2π , this can also be written as

8mL2 c
λ=
5h
12 MODULE 4. APPLICATIONS OF QUANTUM MECHANICS

Final Result

5π 2 ℏ2 8mL2 c
Eγ = , λ =
2mL2 5h
This is the wavelength of the photon emitted when the particle transitions from the
n = 3 state to the n = 2 state in a one–dimensional infinite potential well.

4.2 Extension to the Three-Dimensional Case

4.2.1 The Potential
In three dimensions, the infinite square well (or box ) with cubic symmetry is defined as
(
0, 0 ≤ x, y, z ≤ a,
V (x, y, z) =
∞, otherwise.
Thus the particle is confined within a cube of side length a.

4.2.2 Separation of Variables

Inside the cube, the time-independent Schrödinger equation is
ℏ2 ∂ 2 Ψ ∂ 2 Ψ ∂ 2 Ψ
 
− + + = EΨ.
2m ∂x2 ∂y 2 ∂z 2
We seek separable solutions of the form
Ψ(x, y, z) = X(x)Y (y)Z(z).
Substituting and dividing by X(x)Y (y)Z(z) give
1 d2 X 1 d2 Y 1 d2 Z 2mE
2
+ 2
+ 2
=− 2 .
X dx Y dy Z dz ℏ
Each term must be a constant:
d2 X d2 Y d2 Z
2
= −kx2 X, 2
= −ky2 Y, 2
= −kz2 Z,
dx dy dz
with
ℏ2
kx2 + ky2 + kz2 .


E=
2m

4.2.3 Boundary Conditions and Solutions

The boundary conditions are
X(0) = X(a) = 0, Y (0) = Y (a) = 0, Z(0) = Z(a) = 0.
Thus the solutions are
r r r
2  nx πx  2  ny πy  2  nz πz 
Xnx (x) = sin , Yny (y) = sin , Znz (z) = sin ,
a a a a a a
where nx , ny , nz = 1, 2, 3, . . .
4.3. QUANTUM TUNNELING 13

4.2.4 Wavefunctions and Energies

The normalized eigenfunctions of the 3D cube are
 3/2 
2 nx πx   ny πy   nz πz 
Ψnx ,ny ,nz (x, y, z) = sin sin sin ,
a a a a
with corresponding energies
ℏ2 π 2 2 2 2


Enx ,ny ,nz = nx + n y + nz .
2ma2

4.2.5 Degeneracy
Because the energy depends only on the sum of squares n2x + n2y + n2z , different triplets
(nx , ny , nz ) can yield the same energy. For example,

(nx , ny , nz ) = (1, 1, 2), (1, 2, 1), (2, 1, 1)

all correspond to the same energy level. This threefold degeneracy is a direct consequence
of the cubic symmetry of the potential.

4.3 Quantum Tunneling

Quantum tunnelling through a rectangular barrier
In classical mechanics, if a particle of energy E encounters a potential barrier of height
U > E, it is completely reflected; the barrier is impenetrable. However, in quantum
mechanics, the particle is described by a wavefunction that extends into the classically
forbidden region. As a result, there exists a finite probability for the particle to penetrate
the barrier and emerge on the other side - a purely quantum effect known as tunnelling.

Potential barrier and setup

Consider a particle of mass m and energy E incident from the left on a one-dimensional
rectangular potential barrier of height U and width L:


 0, x < 0 (Region I)

V (x) = U, 0 ≤ x ≤ L (Region II)


0, x > L (Region III)


We assume E < U , i.e., the particle energy is less than the potential height.

Time-independent Schrödinger equation. In each region, the stationary wavefunc-

tion ψ(x) satisfies
ℏ2 d2 ψ
− + V (x)ψ = Eψ.
2m dx2
This can be written as
d2 ψ 2m
+ 2 (E − V (x))ψ = 0.
dx2 ℏ
14 MODULE 4. APPLICATIONS OF QUANTUM MECHANICS

Solutions in different regions

Region I (x < 0, V = 0):
√
d2 ψ 2mE
2
+ k12 ψ = 0, k1 = .
dx ℏ
The general solution is a superposition of incident and reflected waves:

ψI (x) = eik1 x + r e−ik1 x .

Here r is the reflection amplitude.

Region II (0 ≤ x ≤ L, V = U ):
p
d2 ψ 2m(U − E)
− k22 ψ = 0, k2 = .
dx2 ℏ
Since E < U , the term (E − U ) is negative, making k2 real and positive. Hence the
solution is no longer oscillatory, but exponential:

ψII (x) = A ek2 x + B e−k2 x .

This describes a wave that decays (and grows) exponentially within the barrier. The
decaying part represents the evanescent wave - a nonzero amplitude within the classically
forbidden region.

Region III (x > L, V = 0):

d2 ψ
+ k12 ψ = 0,
dx2
giving a transmitted wave:
ψIII (x) = t eik1 x ,
where t is the transmission amplitude.

Boundary conditions
dψ
At x = 0 and x = L, both ψ and dx
must be continuous:

ψI (0) = ψII (0), ψI′ (0) = ψII′ (0),

ψII (L) = ψIII (L), ψII′ (L) = ψIII
′
(L).

Solving these four equations for r, t, A, B yields (after some algebra) the transmission
probability:
−1
U 2 sinh2 (k2 L)

2
T = |t| = 1 + .
4E(U − E)
This is the exact quantum-mechanical transmission coefficient for a rectangular barrier.
4.3. QUANTUM TUNNELING 15

Opaque-barrier approximation
If the barrier is thick or high so that k2 L ≫ 1, then
sinh(k2 L) ≈ 21 ek2 L .
Substituting in the exact formula gives
p !2
4 E(U − E)
T ≈ e−2k2 L .
U

For qualitative estimates, the prefactor is often neglected, yielding the approximate ex-
ponential dependence:
p
−2k2 L 2m(U − E)
T ∝e , k2 = .
ℏ
Thus, the transmission probability falls off exponentially with both the width and the
height of the potential barrier.

Figure 4.3: Rectangular barrier of height U and width L. A particle of energy E < U
has a finite probability of tunnelling through the barrier. (Adapted from Modern Physics
by Arthur Beiser, 6th edition, for instructional use only.)

Example: Scanning Tunneling Microscope (STM). The STM operates on the

principle of quantum tunneling. When a sharp metallic tip is brought extremely close (a
few Angstroms) to a conducting surface, electrons can tunnel through the vacuum gap
between them, producing a measurable tunneling current.
The tunneling current I depends sensitively on the separation L as
√
−2k2 L 2mϕ
I∝e , k2 = ,
ℏ
16 MODULE 4. APPLICATIONS OF QUANTUM MECHANICS

where ϕ is the effective work function (barrier height).

Because of this exponential dependence, a change in distance of even 0.1 nm can
change the current by an order of magnitude, allowing the STM to resolve surface features
with atomic precision.

Summary
• Quantum tunnelling arises from the wave nature of matter and the continuity of
the wavefunction.

• The probability of transmission through a barrier of height U and width L is

−1
U 2 sinh2 (k2 L)

T = 1+ .
4E(U − E)

• For k2 L ≫ 1, T ≈ e−2k2 L .

• Applications include α-decay, STM, tunnel diodes, and field emission.