Dr.

Tarun Garg

APPLICATIONS OF QUANTUM MECHANICS Assistant Professor

Department of Physics
VIT Vellore
 SYLLABUS AND REFERENCE BOOKS
Syllabus:
Eigenvalues and eigenfunction of particle confined in one dimensional box - Basics of
nanophysics - Quantum confinement and nanostructures - Tunnel effect (qualitative) and
scanning tunneling microscope.

Reference Books:
1. Arthur Beiser, Concepts of Modern Physics; Sixth Edition (2020), McGraw Hill Publication.
2. Raymond A. Serway, Clement J. Mosses, Curt A. Moyer Modern Physics, 2010, 3rd Indian
Edition Cengage learning.
 PARTICLE IN AN INFINITE SQUARE-WELL POTENTIAL
(1-DIMENSIONAL BOX)
The simplest such system is a particle trapped in a 1-D box with infinitely hard walls that the particle
cannot penetrate. This potential is called an infinite square well and is given by:

0 0<𝑥<𝐿
𝑈 𝑥 =ቊ
∞ 𝑥 ≤ 0, 𝑥 ≥ 𝐿

• We may specify the particle’s motion is restricted to traveling along the x axis
between x = 0 and x = L by infinitely hard walls.
• A particle does not lose energy when it collides with such walls, so that its total
energy stays constant. The potential energy U of the particle is infinite on both
sides of the box, while U is a constant-say 0 for convenience on the inside (Fig).
• As the particle cannot have an infinite amount of energy, it cannot exist outside A square well potential with
the box, and so its wave function 𝜓 is 0 for x ≤ 0 and x ≥ L. infinitely high barriers at
each end corresponds to a
• Our task is to find what is 𝜓 within the box, namely, between x = 0 and x = L. box of infinitely hard walls
 CONT’D….
𝑑 2 𝜓 2𝑚
Within the box Schrödinger’s equation becomes + 𝐸−𝑈 𝑥 𝜓 𝑥 =0 (1)
𝑑𝑥 2 ħ2
It is to be noted that in this problem potential energy does not depend on time. In fact we have assumed,
U=0 inside the box, so Schrodinger’s time independent equation would be applicable in this case.

𝑑 2 𝜓 2𝑚
Therefor equation (1) will reduce to: + 2 𝐸𝜓 = 0
𝑑𝑥 2 ħ
𝑑2 𝜓
or + 𝑘 2𝜓 = 0 (2)
𝑑𝑥 2
We can get this using de Broglie's
2𝑚𝐸 2𝑚𝐸 ℎ ℎ 2𝜋
Where, 𝑘 2 = or 𝑘 = formula, λ = 𝑚𝑣 = 2𝑚𝐸 and 𝑘 =
ħ2 ħ λ

The general solution to the equation (2) is 𝜓 = 𝐴 sin 𝑘𝑥 + 𝐵 cos 𝑘𝑥 (3)

Here A and B are constants and can be found using boundary conditions.
 CONT’D….
Boundary conditions of the potential dictate that the wave function, 𝜓 must be zero at 𝑥 = 0 and 𝑥 = 𝐿.
Using 1st boundary condition, when 𝑥 = 0 then 𝜓=0
From equation (3), we get 0 = 𝐴 sin 0 + 𝐵 cos 0
Which implies 𝐵 = 0
Thus the wave function, 𝜓 becomes 𝜓 = 𝐴 sin 𝑘𝑥
Using 2nd boundary condition, when 𝑥 = 𝐿 then 𝜓 = 0
From equation (4), we get 0 = 𝐴 sin 𝑘𝐿
This yields valid solutions for integer values of n such that:
𝑘𝐿 = 𝑛𝜋 (5) Where 𝑛 = 1, 2, 3, 4 … . .

𝑛𝜋𝑥
Therefore the wave function is now 𝜓𝑛 (𝑥) = 𝐴 sin Expression of eigen function of the particle
𝐿
 CONT’D….
Still we have to find the constant A which can be found by normalizing the wave function
∞
According to normalization condition in 1-dimension, ‫׬‬−∞ ψ 2 𝑑𝑥 = 1
Now
𝑛𝜋𝑥
𝜓𝑛 2 =𝜓𝑛 𝜓𝑛 ∗= 𝐴2 𝑠𝑖𝑛2
𝐿
(As given wave function is a real one so its multiplication with its complex conjugate will yield square of
the function itself)
𝐿
𝑛𝜋𝑥
∴ න 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = 1
𝐿
0

𝐿 𝐿 2𝑛𝜋𝑥 𝐿
𝑛𝜋𝑥 1 − cos 𝐴2 2𝑛𝜋𝑥
𝐿
∴ 𝐴2 න 𝑠𝑖𝑛2 𝑑𝑥 = 1 ⇒ 𝐴2 න 𝑑𝑥 = 1 ⇒ න 1 − cos 𝑑𝑥 = 1
𝐿 2 2 𝐿
0 0 0
 CONT’D….
𝑛=3
𝐴2 𝐿 2𝑛𝜋𝑥 𝐿
On integrating w.r.t. x, we get 𝑥− 𝑠𝑖𝑛 =1
2 2𝜋𝑛 𝐿 0
𝑛=2
𝐴2 2
On substituting the limits, we get, 𝐿 = 1 ⇒ 𝐴2 =
2 𝐿

2 𝑛=1
∴𝐴=
𝐿

2 𝑛𝜋𝑥 Expression for eigen function

Thus the normalized wave function becomes, 𝜓𝑛 = sin of the particle
𝐿 𝐿

These functions are identical to those obtained for a vibrating string with fixed ends.
 QUANTIZED ENERGY OF THE PARTICLE- ENERGY EIGEN VALUES
From equation (5), 𝑘𝐿 = 𝑛𝜋

The quantized wave number and hence energy becomes

𝑛𝜋 2𝑚𝐸𝑛 𝑛2 𝜋 2 ħ2 Expression for Energy

𝑘𝑛 = = ⇒ 𝐸𝑛 = Eigen Values
𝐿 ħ 2𝑚𝐿2

Note that the energy depends on the integer values of n. Hence the energy is quantized and non-zero.
𝜋 2 ħ2
The case of 𝑛 = 1 is called the ground state energy. 𝐸1 = Which is very small however non-zero.
2𝑚𝐿2
For 𝑛 = 2, 4𝜋 2 ħ2 For 𝑛 = 3,
𝐸 = or 𝐸2 = 4𝐸1 𝐸3 = 9𝐸1 and so on…
1st excited state 2 2𝑚𝐿2 2nd excited state
 PLOTS OF PROBABILITY DENSITY OF THE PARTICLE
𝜓𝑛 2 =𝜓𝑛 𝜓𝑛 ∗
For 𝑛 = 1, the ground state
2 𝜋𝑥 Probability density
𝜓1 2 = 𝑠𝑖𝑛2 is maximum in the
𝐿 𝐿
middle of the box

For 𝑛 = 2, 1st excited state

Probability density is zero in For 𝑛 = 3, 2nd excited state
2 2𝜋𝑥 the middle of the box as well
𝜓2 2 = 𝑠𝑖𝑛2 2
2 3𝜋𝑥 Probability density is maximum
𝐿 𝐿 𝜓3 = 𝑠𝑖𝑛2
as at the boundaries and 𝐿 𝐿 at L/6, L/2 and 5L/6.
maximum at L/4 and 3L/4
 BARRIERS AND QUANTUM TUNNELING
Consider a particle of energy E approaching a potential barrier of height Vo and the potential
everywhere else is zero.
We will first consider the case when the energy is greater than the potential barrier i.e. 𝐸 > 𝑉𝑜

When 𝐸 > 𝑉𝑜

Particle can comfortably

go over the potential
barrier, No tunnelling
CONT’D….
Classical
wave function
for finite square
well potential
where 𝐸 < 𝑉𝑜

Classically, when an object hits a potential barrier that it doesn’t have enough energy to pass, it will
never go though that potential wall, it always bounces back.

For example, if you throw a ball at a wall, it will bounce back at you.
 QUANTUM TUNNELLING
Now we consider the situation where classically the particle does not have enough energy to surmount the
potential barrier, E < V0.

In quantum mechanics when a particle hits a potential that it doesn’t have enough energy to pass, when
inside the square well, the wave function dies off exponentially.
If the well is short enough, there will be a noticeable probability of finding the particle on the other side.
There is a small, but finite, probability that the particle can penetrate the barrier and even emerge on the
other side. The transmission coefficient through the barrier may be calculated as:

Transmission Coefficient, 𝑇 ≈ 𝑒 −2𝛼𝐿 Where 𝛼 =

2𝑚(𝑉𝑜 −𝐸)
ħ2
 CONT’D….
The transmission coefficient through the barrier may be appx. calculated as:
Transmission Coefficient, 𝑇 ≈ 𝑒 −2𝛼𝐿 2𝑚(𝑉𝑜 −𝐸)
Where 𝛼 =
ħ2
𝐸 𝐸
or 𝑇 = 16 1− 𝑒 −2𝛼𝐿 for αL >>1
𝑉𝑜 𝑉𝑜

Example: A beam of electrons is accelerated through a potential of 5 V toward a potential barrier of

width 0.8 nm and height 10 eV. What fraction of the electrons tunnel through the barrier?
Solution:
Let us determine the value of α first.
2𝑚(𝑉𝑜 − 𝐸) 2 × 9.1 × 10−31 (10 − 5) × 1.6 × 10−19 × 4 × (3.14)2 −10 𝑚−1
𝛼= = = 1.15 × 10
ħ2 (6.63 × 10−34 )2
Thus, αL=1.15 × 10−10 × 0.8 × 10−9 = 9.2
5 5
Which gives, 𝑇 = 16 1− 𝑒 −2×9.2 = 4.1 × 10−8
10 10
EXAMPLE 1: ANALOGY WITH WAVE OPTICS
•If light passing through a glass prism reflects from an internal surface with an angle
greater than the critical angle, total internal reflection occurs.
•However, the electromagnetic field is not exactly zero just outside the prism.
•we bring another prism very close to the first one, experiments show that the (a)
electromagnetic wave (light) appears in the second prism.
•The situation is analogous to the tunneling described here. This effect was observed
by Newton and can be demonstrated with two prisms and a laser.
•The intensity of the second light beam decreases exponentially as the distance
between the two prisms increases.

(b)

14
 EXAMPLE 2:ALPHA-PARTICLE DECAY
•The phenomenon of tunneling explains the alpha-particle decay of heavy,
radioactive nuclei.
•Inside the nucleus, an alpha particle feels the strong, short-range attractive
nuclear force as well as the repulsive Coulomb force.
•The nuclear force dominates inside the nuclear radius where the potential is
approximately a square well.
•The Coulomb force dominates outside the nuclear radius.
•The potential barrier at the nuclear radius is several times greater than the
energy of an alpha particle.
•According to quantum mechanics, however, the alpha particle can
“tunnel” through the barrier.
•Hence this is observed as radioactive decay. 15
APPLICATIONS OF QUANTUM TUNNELLING:
SCANNING TUNNELLING MICROSCOPE
• Scanning Tunneling Microscopy, or STM, is an
imaging technique used to obtain ultra-high
resolution images at the atomic scale, without using
light or electron beams.
• It is used to study the 3-D topography of
conducting surfaces
• STM was invented in 1981 by two IBM scientists
named Gerd Binnig and Heinrich Rohrer.
• Five years later, the invention earned them the
Nobel Prize in Physics. Schematic of a Scanning Tunnelling Microscope
16
 STM IMAGE

Resolution:~0.01 nm.

• Silicon surface atoms enlarged 20 million times, color-enhanced by computer.

• The world's first images of individual surface atoms and the bonds that hold them in
place were produced by a research technique developed by IBM -- scanning tunneling
microscopy
 WORKING PRINCIPLE OF STM
• Scanning tunneling microscope (STM) is a powerful technique for
viewing surfaces at the atomic level.
• STM probes the electronic density of states of a material using
tunneling current.
• The STM is based on the concept of Quantum Tunneling.
• An extremely fine conducting probe is held about an atom’s diameter
from the sample.
• Electrons tunnel between the surface and the tip, producing an
electrical signal.
• While it slowly scans across the surface, the tip is raised and
lowered in order to keep the signal constant and maintain the
distance.
• This enables it to follow even the smallest details of the surface it is
scanning.
CONT’D….

• A STM does not measure nuclear position directly. Rather it measures the electron
density clouds on the surface of the sample.
• In some cases, the electron clouds represent the atom locations pretty well, but not
always.
 OPERATING MODES OF STM
The STM operates in two distinct modes: constant height mode and constant current mode.

• Constant height mode is generally used when the sample surface is very smooth.
• In this mode, the probe tip stays at a set height while it quickly raster scans across the
sample.
• By measuring changes in the intensity of the tunneling current as a function of (x, y)
position and bias voltage, researchers can construct an image of the electronic density
of states of the sample surface, defects, frontier molecular orbitals, and more.

20
 CONSTANT CURRENT MODE
• The more popular mode is known as the constant current mode.
• In this mode, the tunneling current is held constant by the use of a feedback loop
system that adjusts the distance between the tip and the surface.
• That is to say, if the tunneling current exceeds the target value, the feedback
control system will increase the distance between the tip and the sample; if the
tunneling current is less than the target current value, the feedback control system
will bring the tip closer to the surface of the sample.
• The resulting three-dimensional distance profile as a function of (x, y) position
can help researchers measure a wide array of characteristics, including surface
roughness, defects, and the size and conformation of molecules on the surface.
21
NANOMATERIALS
•Top-down Science
•Bottom-up Science

Nanomaterials are the materials possessing grain sizes of the order of a

billionth of a meter (10-9m).

Nanomaterial research literally exploded in mid -1980’s

 TYPICAL SIZE OF SMALL PARTICLES
Tobacco
mosaic
Virus Hepatitis B
Virus

Bacteria Pollen
Nanoparticles
Human Hair

Soot
A Scanning
electron
microscope
image of a hair Carbon black
strand
0.001 0.01 0.1 1 10 100 1000
Particle size (µm)
CONT’D….
❖Conventional material have grain size anywhere from 100 µm to 1mm and more
❖Particles with size between 1-100 nm are normally regarded as Nanomaterials
❖The average size of an atom is of the order of 1-2 Angstroms in radius.
❖1 nanometer =10 Angstroms
❖1 nm there may be 3-5 atoms
WHAT MAKES A NANOMATERIAL DIFFERENT FROM BULK?
Two principal factors cause the properties of nanomaterials to differ significantly from Bulk materials:
• Increased relative surface area
• Quantum effects
These factors can change or enhance properties such as chemical reactivity, strength, magnetic, thermal
and electrical properties.
Surface Effects:
As a particle decreases in size, a greater proportion of atoms are found at the surface compared to
those inside. For example, a particle of
Size-30 nm-> 5% of its atoms on its surface
Size-10 nm->20% of its atoms on its surface
Size-3 nm-> 50% of its atoms on its surface
Nanoparticles are more reactive than large particles.
 CLASSIFICATION OF NANOMATERIALS
❖

•Nanomaterials are those materials which have structured components with at

least one dimension less than 100 nm.
•One dimension in nanoscale (Other two dimensions are extended) (2-D) e.g.
Thin films, Surface Coatings, Computer chips
•Two dimensions in nanoscale (Other one dimension is extended) (1-D) e.g.
Nanowires, Nanotubes
•Three dimensions squeezed to nanoscale (0-D) e.g. Nanoparticles, Precipitates,
Colloids, Quantum dots (tiny particles of semiconductor material)
 QUANTUM CONFINEMENT
• Quantum confinement can be observed once the diameter of a material is of the same
magnitude as the de Broglie wavelength of the electron wave function.
• When materials are this small, their electronic and optical properties deviate
substantially from those of bulk materials.
• A particle behaves as if it was free when the confining dimension is large compared to
the wavelength of the particle.
• During this state, the band gap remains at its original energy due to a continuous
energy state. However, as the confining dimension decreases and reaches a certain
limit, typically in nano scale, energy spectrum becomes discrete.
• As a result, the band gap becomes size-dependent. This ultimately results in a blue
shift in light emission as the size of the particles decreases.
27
EXAMPLE: GOLD NANO PARTICLES

Different sizes gold nano particles appear of

different colors. As the size of the particle is reduced,
the wavelength of the light emitted by the particle
decreases due to increase in energy band gap.
DENSITY OF STATES IN 3-D, 2-D, 1-D, 0-D NANO MATERIALS
 HOW TO MAKE QUANTUM WELL, WIRE AND DOT STRUCTURES?
Quantum wire

Quantum well

Quantum dot
DENSITY OF STATES AS A FUNCTION OF ENERGY