Module 4 (BAPHY105)

Applications of Quantum Mechanics

Dr. Gopal Kashyap

Contents
1 Particle in a One-Dimensional Box (Infinite Potential Well) 1
1.1 Boundary Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Energy Eigenvalues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Normalization of the Wave Function . . . . . . . . . . . . . . . . . . . . 3
1.4 Transitions in a 1D Infinite Potential Box . . . . . . . . . . . . . . . . . . 4

2 Extension to a Three-Dimensional Infinite Potential Box 5

2.1 Schrödinger Equation and Separation of Variables . . . . . . . . . . . . . 5
2.2 Eigenfunctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3 Energy Eigenvalues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4 Degeneracy in a Three-Dimensional Infinite Potential Box . . . . . . . . 6

3 Quantum Tunneling Effect 10

1 Particle in a One-Dimensional Box (Infinite Poten-

tial Well)

Consider a particle of mass m moving along the x-axis

between two rigid walls at x = 0 and x = L. The particle
is free to move between the walls. The potential energy of
the particle inside the box is zero and no force acts on it.
The particle does not lose energy when it strikes the walls,
because the walls are infinitely rigid. The potential energy
function U (x) is therefore
(
0, 0 < x < L,
U (x) = (1)
∞, x ≤ 0 or x ≥ L. Figure 1: One-dimensional
infinite potential well.
The wave function ψ(x) is obtained by solving the one-
dimensional time-independent Schrödinger equation
d2 ψ 2m  
+ E − U (x) ψ = 0. (2)
dx2 ℏ2
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Since U (x) = 0 inside the box,
d2 ψ 2mE
+ 2 ψ = 0. (3)
dx2 ℏ
Since,
2mE = p2
2mE p2
⇒ = = k2
ℏ2 ℏ2
where k = 2π/λ, is the wavevector. So the equation (3) can be written as
d2 ψ(x)
+ k 2 ψ(x) = 0. (4)
dx2
The general solution of this equation is given by
ψ(x) = A sin(kx) + B cos(kx), (5)
where A and B are constants and
r
2mE
k= . (6)
ℏ2

1.1 Boundary Conditions

For a physically acceptable wavefunction, it must be continuous at the boundaries. In
our case, the particle is confined between the walls at x = 0 and at x = L, which means
wavefunction must vanish outside the region (x < 0 and x > L). Therefore, the boundary
conditions are

ψ(0) = 0 and ψ(L) = 0. (7)

At x = 0,
ψ(0) = A sin(0) + B cos(0) = B = 0.
Thus B = 0 and the wavefunction simplifies to
ψ(x) = A sin(kx).
At x = L,
ψ(L) = A sin(kL) = 0.
For a nontrivial solution (A ̸= 0), we require
sin(kL) = 0 ⇒ kL = nπ,
where n = 1, 2, 3, . . . is called the principle quantum number.
Hence, the allowed wave numbers are
nπ
k= , n = 1, 2, 3, . . . (8)
L
and the corresponding wavefunction are
 nπx 
ψn (x) = A sin . (9)
L
Note that n = 0 is excluded, as it leads to the trivial solution ψ0 (x) = 0 for all values of
x.
From k = nπ/L, we see that only specific wave numbers (and hence wavelengths)
are allowed, leading to the quantization of the wavelength, similar to the formation of
standing waves on a string fixed at both ends.

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1.2 Energy Eigenvalues
2mE
From the quantization conditions, k 2 = we get
ℏ2
ℏ2 k 2 ℏ2  nπ 2
En = = , n = 1, 2, 3, . . . (10)
2m 2m L
Or
n2 π 2 ℏ2
En = (11)
2mL2
Thus, En ∝ n2 .
Each allowed energy En is an energy eigenvalue, and the corresponding ψn (x) is an
eigenfunction. The integer n is the quantum number, it determines the allowed en-
ergy levels and the number of nodes in the wavefunction. Therefore, the energy spectrum
consists of discrete levels, with spacing that depends on the box length L. This shows
that the energy of a particle in an infinite potential well is quantized.

1.3 Normalization of the Wave Function

As the probability of finding the particle inside the box must be unity, i.e.,
Z L
|ψn (x)|2 dx = 1. (12)
0
 nπx 
Substituting ψn (x) = A sin ,
L
Z L  nπx 
2
A sin2
dx = 1, (13)
L 0
A2 L 
Z
2 nπx
 
1 − cos dx = 1, (14)
2 0 L
 
2 L
A = 1, (15)
2
r
2
A= . (16)
L
Therefore, the normalized wave function is given by
r
2  nπx 
ψn (x) = sin . (17)
L L

The probability density |ψn (x)|2 gives the likelihood of finding the particle at position
x inside the box.
2  nπx 
|ψn (x)|2 = sin2 . (18)
L L
The first few wave functions ψn (x), n = 1, 2, 3, 4, and corresponding probability den-
sity |ψn (x)|2 are plotted in the Fig.[2].

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Figure 2: Normalization wavefunction and probability densities for first four eigenstates.

1.4 Transitions in a 1D Infinite Potential Box

Consider an electron confined in a one-dimensional infinite potential well (box) of length
L. The energy eigenvalues of the electron are given by
n2 π 2 ℏ2
En = , n = 1, 2, 3, . . . , (19)
2mL2

Photon Emission
When the electron transitions from a higher energy level ni to a lower energy level nf
(ni > nf ), it emits a photon of energy
π 2 ℏ2
n2i − n2f .


Ephoton = Eni − Enf = 2
(20)
2mL
The corresponding wavelength of the emitted photon is
hc
λ= , (21)
Ephoton
where h is Planck’s constant and c is the speed of light.

Photon Absorption
Conversely, if a photon of energy Ephoton is absorbed by the electron, it can induce a
transition from a lower energy level ni to a higher energy level nf (nf > ni ), provided
that
π 2 ℏ2 2 2


Ephoton = Enf − Eni = n f − n i . (22)
2mL2

2 Extension to a Three-Dimensional Infinite Poten-

tial Box
The one-dimensional infinite potential well can be generalized to three dimensions by
considering a particle confined inside a box of side Lx , Ly , Lz , where the potential is

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defined as (
0, 0 < x < Lx , 0 < y < Ly , 0 < z < Lz ,
V (x, y, z) = (23)
∞, otherwise.

2.1 Schrödinger Equation and Separation of Variables

The time-independent Schrödinger equation in three dimensions is

ℏ2
 2
∂2 ∂2

∂
− + + ψ(x, y, z) = Eψ(x, y, z). (24)
2m ∂x2 ∂y 2 ∂z 2

Since the potential is separable, we can write the wavefunction as a product of three
functions, each depending on a single coordinate:

ψ(x, y, z) = X(x) Y (y) Z(z). (25)

Substituting this into the Schrödinger equation and separating variables gives three
independent 1D equations:

ℏ2 d2 X
− = Ex X, (26)
2m dx2
ℏ2 d2 Y
− = Ey Y, (27)
2m dy 2
ℏ 2 d2 Z
− = Ez Z, (28)
2m dz 2
with
E = Ex + Ey + Ez . (29)

2.2 Eigenfunctions
Applying the boundary conditions ψ = 0 at the walls (x = 0, Lx ; y = 0, Ly ; z = 0, Lz ),
the normalized eigenfunctions are
r s r      
2 2 2 nx πx ny πy nz πz
ψnx ,ny ,nz (x, y, z) = sin sin sin , (30)
Lx Ly Lz Lx Ly Lz

where nx , ny , nz = 1, 2, 3, . . . are the quantum numbers along each axis.

2.3 Energy Eigenvalues

The corresponding energy eigenvalues are

π 2 ℏ2 n2x n2y n2z

 
Enx ,ny ,nz = + + . (31)
2m L2x L2y L2z

For the case of cubic infinite potential, Lx = Ly = Lz = L

π 2 ℏ2
n2x + n2y + n2z .


Enx ,ny ,nz = 2
(32)
2mL

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Ground state: nx = ny = nz = 1 with corresponding eigenfunction ψ1,1,1 (x, y, z) and
energy eigenvalue
3π 2 ℏ2
E1,1,1 = (33)
2mL2
First excited state: (nx , ny , nz ) = (1, 1, 2), (1, 2, 1), (2, 1, 1) with corresponding eigen-
functions ψ1,1,2 (x, y, z), ψ1,2,1 (x, y, z), ψ2,1,1 (x, y, z) and energy eigenvalue is same for all
three eigenfunctions
6π 2 ℏ2
E1,1,2 = E1,2,1 = E2,1,1 = . (34)
2mL2

2.4 Degeneracy in a Three-Dimensional Infinite Potential Box

The corresponding energy eigenvalues are

ℏ2 π 2 n2x n2y n2z

 
Enx ny nz = + + .
2m L2x L2y L2z

Degeneracy occurs when different combinations of quantum numbers (nx , ny , nz )

yield the same total energy E.
If the box is cubical (Lx = Ly = Lz = L), the energy becomes

ℏ2 π 2 2
Enx ny nz = (n + n2y + n2z ).
2mL2 x
Thus, the energy depends only on the sum of the squares of the quantum numbers:

n2 = n2x + n2y + n2z .

Different sets of (nx , ny , nz ) that give the same n2 correspond to the same energy and
are therefore degenerate.

Example: Degenerate Levels

Level Quantum Numbers (representative) n2 = n2x + n2y + n2z Degeneracy

Ground state (1,1,1) 3 1
1st excited (1,1,2) and permutations 6 3
2nd excited (1,2,2) and permutations 9 3
3rd excited (1,1,3) and permutations 11 3
4th excited (2,2,2) 12 1
5th excited (1,2,3) and permutations 14 6
6th excited (2,2,3) and permutations 17 3

Remarks
ˆ Degeneracy arises due to the symmetry of the potential.

ˆ For a cubical box, permutation of quantum numbers corresponds to physically

equivalent states.

ˆ If the box is rectangular (Lx ̸= Ly ̸= Lz ), degeneracy is broken because energy

depends on each length separately.

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 ˆ Degeneracy plays an important role in the statistical and quantum properties of
systems, such as in atomic orbitals or electron energy levels in solids.

Degeneracy in 3D box ⇒ same energy, different quantum states.

Example:
ℏ2 π 2
Find the degeneracy of the level E = × 14.
2mL2
n2x + n2y + n2z = 14.

Possible combinations: (1, 2, 3) and its permutations ⇒ 6 states. Hence, the degeneracy
is 6.

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 Quantum Tunneling Effect

Quantum tunneling is a phenomenon in
which particles penetrate a potential energy
barrier with a height greater than the total
energy of the particles.


The phenomenon is interesting and important
1926, Erwin Schrodinger
because it violates the principles of classical
mechanics.


Quantum tunneling is important in models of
the Sun and has a wide range of applications,
such as the scanning tunneling microscope
and the tunnel diode

1

In the language of quantum mechanics, the hill
is characterized by a potential barrier. A finite-
height square barrier is described by the
following potential-energy function:

2

The stationary Schrӧdinger equation has the
following forms in these three regions

3
The continuity condition at region boundaries requires that: at x=0

and

Also at x=L

4
We can easily verify that in regions I and
III, the solutions must be in the following general forms:

G=0
As there will be no
reflection in region
III

where k = √2mE /ħ is a wave number

5
The amplitude of the incident wave is

Similarly the refelected wave is: |ψref (x)|2 = |B|2 , and the

amplitude of the transmitted wave is |ψtran (x)| = |F |2

6
The transmission probability or tunneling probability is the ratio of
the transmitted intensity |F |2 to the incident intensity |A|2 , written as:

2
|F|
T= 2
| A|

And Reflection probability R is defined

2
as: |B|
R= 2
| A|
Such that R+T=1

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 • In region II, Schrodinger equation can be rearranged to

The general solution to this Equation is not oscillatory (unlike in the other regions)
and is in the form of exponentials that describe a gradual attenuation of ψ II (x)

8
 
We Apply the boundary
conditions to find equations for
• the unknown constants


The transmission probability
that describes the phenomenon
of tunneling is

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 Measuring the position and momentum of an electron

• For a wide and high barrier that



transmits poorly, the

transmission probability can be
approximated by

Wave length of approaching particle should be in the

same order of the length of the tunneling barrier

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 Tunneling Applications
•

Alpha decay
• Nuclear Fusion and Fission Process
• Tunnel Diode
• Quantum Computing
• Scanning Tunnelling Microscope (STM)

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 
Problem

1. Two silver nanowires are insulated by a oxide nano-layer that provides a 20.0 eV potential barrier.
Estimate the tunneling probability between the nanowires by 10.00-eV electrons through a 8.00 nm thick
oxide layer. What if the thickness of the layer were reduced to just 4.00 nm? What if the energy of
electrons were increased to 18.00 eV?

Take, m=511 keV/c2, ħ = 0.1973 keV ⋅ nm/c

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