MODULE-2

QUANTUM MECHANICS
Quantum Mechanics is a new branch of study in physics which is
indispensable in understanding the mechanics of particles or bodies in the
atomic and the subatomic scale. The term quantum mechanics was first
introduced by Max Born in1924.Within the field of engineering, quantum
mechanics plays an important role. The study of quantum mechanics has lead to
many new inventions that include the laser, the diode, the transistor, the
electron microscope, and magnetic resonance imaging. Flash memory chips
found in USB drives also use quantum ideas to erase their memory cells. The
entire science of Nanotechnology is based on the quantum mechanics.

WAVE PARTICLE DUALISM:

The nature of light is not unique i.e. it exhibits both particle nature and wave
nature.
Some phenomenon like interference, Diffraction and Polarization can be
explained on the basis of Wave nature of light while other phenomenon like
photoelectric effect and Compton Effect can be explained on the basis of particle
nature of light. This property where light behaves both as waves and particles is
called dual nature of light or wave particle dualism
Example- X-rays assumes the status of the particles in the Compton Effect
experiment and the same X-rays get diffracted by a crystal in few other
experiments.

De- BROGLIE’S HYPOTHESIS:

Because of the dual nature observed of radiation and light, Louis de Broglie
put forward a bold hypothesis. He reasoned out that nature exhibits a great
amount of symmetry. “If the radiation behaves as waves sometimes and as
particles at other times then it is expected that entities such as electrons which
behave as particles should also exhibit wave like behavior under appropriate
circumstances”. This is known as de Broglie’s hypothesis.
According to this Hypothesis, all material particles in motion are associated with
a wave. The waves associated with material particles are called matter waves
or de Broglie waves.

De- BROGLIE WAVELENGTH:

According to de Broglie hypothesis, a moving particle is associated with a wave.
The waves associated with the particles of matter like electrons are known as
matter waves or de Broglie waves.
When a particle has momentum ‘p’, its motion is associated with  called De
Broglie wavelength. It is given by
 h h
= 
p mv
The above equation is known as de Broglie wave equation.
Hence de Broglie wavelength depends upon the mass of the particle and its
velocity.

De Broglie wavelength in different forms

Consider a photon of mass ‘m’ moving with velocity ‘v’, the energy of photon is
given by Einstein mass energy relation as follows

E=mc2 (1)

According to Plank’s theory of radiation, the energy of photon with frequency 𝛾

is given by E=h 𝛾 (2)

Equating equations 1 and 2

mc2 = h 𝛾
𝑐 ℎ𝑐 ℎ
But 𝛾 = hence mc2 =γ= or 𝜆 = but momentum p=m X c
𝜆 𝜆 𝑚𝑐

ℎ
Therefore 𝜆 = this is known as DeBroglie wavelength
𝑝

ℎ
𝜆=
√2𝑚𝑒𝑣
ℎ
𝜆=
√2𝑚𝐸

PHASE VELOCITY AND GROUP VELOCITY:

Phase Velocity ( vphase):
Phase velocity is the velocity of the individual waves. The velocity with which
each phase in a wave moves is called the phase velocity.
If we consider a point to be marked on a travelling wave, then that point
represents a particular phase of the wave, and the velocity with which it is
transported owing to the motion of the wave is called Phase velocity.

π
Here, the point on the wave represents the phase
2
Phase velocity is given by

vphase =
k
Where ω is the angular frequency and k is the wave number.
Group Velocity (vgroup):
When a group of two or more waves of different wavelengths and different
velocities are superimposed on each other, the amplitude of the resultant wave
is varied, which forms a wave group or wave packet. The velocity with which the
envelope enclosing the wave packet is transported is called the group velocity.
In other words the velocity with which the energy in the wave group is
transmitted is called group velocity. Group Velocity is represented by
d
vgroup =
dk
where dω is the change in angular frequency dk is the change in wave number.

Individual waves Wave packet

CHARACTERISTICS OF MATTER WAVES:

[1]Matter waves are the waves that are associated with a moving particle.
The wavelength and energy of the matter waves are given by.
h
= and E = h υ
p
Where, p is the momentum of the particle and υ is the frequency of the
waves.
(2) Group velocity of the matter waves is equal to the velocity of the moving
particle.
(3) Phase Velocity of the matter waves is greater than the velocity of the
Light (c).
c2 c2
We have vphase =  c
V group V
(4) Phase Velocity of different matter waves may be different.
(5) The amplitude of the matter waves at a particular region and time
Depends on the probability density of the particle at that region and time.

HEISENBERG’S UNCERTAINTY PRINCIPLE:

One of the fundamental principles of quantum mechanics is the “Heisenberg’s

uncertainty principle”.
The principle was formulated in 1927 by German physicist Werner Heisenberg.
It is also called the indeterminacy principle.
Statement:
“It is impossible to determine precisely and simultaneously both the
position and momentum of a particle.”
Further, “in any simultaneous determination of the position and
momentum of a particle, the product of the corresponding uncertainties in
the measurement is equal to, or greater than (h/4π)”.
x p  h 4

Where x represents the uncertainty in the measurement of the position of the

particle and p represents the uncertainty in the measurement of its
momentum.
Heisenberg’s uncertainty principle could also be expressed in terms of the
uncertainties involved in the measurement of the physical variable-pair, energy
(E) and time (t) and also angular displacement (θ) and angular momentum
(L).
If E and t are the uncertainties involved in determining the energy and time
respectively, then
E t  h 4

Similarly, if  and L are the uncertainties involved in determining the angular

displacement and angular momentum of the particle respectively, then

 L  h 4
Where, the notation Δ associated with the respective variables indicates the
minimum uncertainty involved in the measurement of the corresponding
variable.
PHYSICAL SIGNIFICANCE OF HEISENBERG’S PRINCIPLE:
 It signifies that one should not think about accurate values for the position
and momentum of a particle. Instead one should think about only the
probable values for the position and momentum.
 The estimation of such probabilities are made by mathematical functions
named probability density functions.

APPLICATION OF HEISENBERG’S UNCERTAINTY PRINCIPLE:

Non-existence of electrons in the nucleus:

As an application of Heisenberg’s uncertainty principle, we consider the case of”

Non-existence of electrons in the nucleus”. This is based on the observations
regarding the emission of β–rays during nuclear decay.
Becquerel demonstrated that β-rays are streams of electrons. During β decay process
it was found that the emitted β-rays travelled with different velocities. Becquerel
demonstrated that β-rays are streams of electrons their kinetic energy varied from
very low values to a maximum value of about 3-4 MeV. Hence the obvious question,
“is it possible that electrons exist inside the nucleus with certain energy, and the
same energy appears as their kinetic energy when they are emitted?”
The proof for this is presented below:
The energy E of a body is expressed as,
𝑝2
E= ------- (1)
2𝑚
Where, m is the mass of the body
P is its momentum
By uncertainty principle,
ℎ
∆𝑥 · ∆𝑝 ≥
4𝜋
h 1
(∆𝑝)x  
4π Δx -------- (2)
Now, for an electron to exist inside the nucleus, the uncertainty Δx in its position
cannot be greater than the nuclear diameter. The nuclear diameter is in the order of
10-14 m. We can take this value to be approximately the maximum space of
confinement. Thus, the maximum value for uncertainty in position can be taken as
(x) ≤ 10-14 m
6.63 1034
∴ ∆𝑝 ≥
4  3.14 1014
(p) x ≥0.5  10-20 Ns
This is the uncertainty in the momentum of the electron. But since the momentum of
the electron must atleast be equal to the uncertainty in the momentum, we can take
(px)x≥ 0.5  10-20 Ns ………..(3)
We know that the rest mass of the electron is m= 9.11 X 10-31 kg
Now by making use of the equation (3 )in equation (1)
(0.5  10 20 )2
∴𝐸≥
2  9.11  1031
𝐸 ≥1.372X10-11 J
Expressing in ev we get
𝐸 ≥1.372X10-11 X 6.24X1018 ev
𝑬 ≥85 Mev.
This means to say that, for electrons to exist inside the nucleus, it must have a
minimum energy of about 85 MeV. But beta-decay studies indicate that the kinetic
energy of β-particles is of the order of 3 to 4 MeV. Hence, we can conclude that
electrons cannot exist inside the nucleus. Value of about 3-4 MeV.
Principle of Complementarity: In 1928, Niels Bohr told this principle of
complementarity. According to this all the objects in atomic dimension requires
description of both wave and particle properties for complete knowledge about it,
however particle and wave behavior are mutually exclusive. This dialecticism in
quantum system is principle of complementarity.
In a situation where the wave aspect of a system is revealed. Its particle aspect is
concealed, and in a situation where the particle aspect is revealed, its wave aspect
is concealed .Revealing both simultaneously is impossible, the wave and particle
aspects are complementary.

Explanation
We know that the consequence of the uncertainty principle is both the wave and
particle nature of the matter cannot be measured simultaneously.in other words, we
can precisely describe the dual nature of light.
 If an experiment is designed to measure the particle nature of the matter,
during this experiment, errors of measurement of both position and the
time coordinates must be zero and hence the momentum, energy and
wave nature of the matter are completely un known.
 Similarly, if an experiment is designed for measuring the wave nature of
the particle, then the errors in the measurement of the energy and the
momentum will be zero, whereas the position and the time coordinates o
the matter will be completely unknown.
From the above explanation, we can conclude that, when the particle nature
of the matter is measured or displayed, the wave nature of the matter is
necessarily suppressed and vice versa.
WAVE FUNCTION:
In quantum mechanics, because of the wave-particle duality, the properties of
particles can be described by a wave. Therefore its quantum state can be
represented by a wave of any arbitrary shape. This is called a Wave function.
The variable quantity characterizing matter waves is known as wave function.
It gives complete information about the system .It is also called state function
as it speaks about the physical state of the system.
Wave function is obtained by solving a fundamental equation called
Schrodinger equation.
 It varies w.r.t position and time.
 It is denoted by a symbol (Ψ)
 Ψ itself cannot be an observable quantity hence, Ψ has no direct physical
significance
 Ψ can have real values or imaginary (complex).

Physical significance of wave function ( ):

a) It gives the idea about the probability of finding a particle.
b) Let us consider a system of electrons. If  is the wave function associated with
that system, then 2 gives measure of density of electrons.
c) If we consider an electron to be present in the region of volume V then
2dV gives the probability of finding the electron in the region of volume dV
d) The certainty of finding the electron in the entire region of volume V is given
by
∫ 2dV = 1.
This is known as normalization.

Probability density:
According to Max born approximation, probability of locating a particle
at a point is directly proportional to  2. This is called probability density.
If  2 = 1; then we are sure that particle is present.
If  2 = 0; then the particle is completely absent.

Consider a particle inside the volume V. Let dV be the infinitesimally small

element in V. If ψ is the wave function associated with the particle, then 2 is
the probability per unit volume of space, centered at a point where ψ is
evaluated at that time
Thus, the probability of finding a particle is
P = ∫ 2 dV
Here, the product of ψ. ψ* is real and is written as  2, where ψ* is the complex
conjugate of ψ.
Probability density is given by
2 =  *, where * is the complex conjugate of.
Normalization of wave function:
Further, if we are certain that the particle is present in a particular region or
space of volume V, then
𝑉 2
∫  . dV = 1
0
This value 1 for probability means, it is clearly a certainty. However, if we are
not certain about locating the particle anywhere in the given volume, then it is
expected to be present somewhere in space. Then the probability of finding the
particle somewhere in the universe must be unity. Thus
 +∞ 2
∫  . dV = 1
−∞

This condition is known as the normalization condition.

A wave function that satisfies the above condition is said to be normalized.
Expectation value:
In Quantum mechanics The expectation value is the probabilistic expected
value of the result of an experiment. It can be thought of as an average of all
the possible outcomes of a measurement as weighted by their likelihood.
Expectation value as such it is not the most probable value of a measurement.in
the real sense the expectation value may have zero probability of occurring. Let
us consider a particle moving along the x axis.
The result of measurement of the position x is a continuous random variable.
Consider a wave function Ψ(x,t). The IΨ(x, t)I 2 .value is probability density for
the position observable and IΨ(x, t)I 2 .dx is the probability of finding the
particle between x and x+dx at time t. Thus, if a measurement of position is
repeated many times in an identical way on an identical particle in identical
circumstance’s, many
Possible outcomes are possible and the expectation value of these out comes is,
according to the following equation
+∞
〈𝑥〉 = ∫−∞ 𝑥 IΨ(x, t)I2 .dx

Eigen function and Eigen value

Eigen functions are those functions which possess the properties of that
they are single valued & finite everywhere and also their first derivatives with
respect to their variables are continuous everywhere..

To find ψ Schrodinger’s wave equation has to be solved. Since it is a second

order differential equation, hence it has many numbers of solutions. But all of
them may not be the correct solutions in such a case we have to choose only a
permitted function. These permitted functions are called Eigen function the
corresponding energy values are called Eigen values
Operator.
An operator (Â) is a symbol or a code which directs one to perform an
operation on the Eigen function (ψ) to get the information (Eigen value)(λ)
Â= λ

Schrodinger’s Wave Equation:

Schrodinger equation is a fundamental wave equation in quantum mechanics
capable of determining the wave function ψ for different physical conditions.
Time independent Schrodinger Wave Equation:
According to de- Broglie theory, for a particle of mass ‘m’ moving with a
velocity ‘v’, the wave length λ is given by,
h h
λ = = ----------------- (1)
p mv

Where, p is the momentum of the particle.

The de- Broglie wave equation for a particle travelling in positive x-direction
can be written in complex form as
Ψ = A ei(kx-ωt) ----------------- (2)
Where, A is the amplitude of the wave, ω is angular frequency of the wave, ψ is
the total wave function and k is the wave number.
The space independent part in equation (2) can be represented as a wave
function,
Ψ = ψA e-iωt ----------------- (3)
Differentiate (3) twice w.r.t. x. Since Ψ depends on x, we get

d 2 d 2
 e  it .        (4)
dx 2 2
dx

Now again differentiate (3) w.r.t. time‘t’ twice, we get

d
 (-iω) Aei(kx-ωt) ψ
dt

d 2
2
= (-iω) (-iω) Aei(kx-ωt) ψ
dt

d 2
2
= -ω2 e-iωt ψ ------------- (5)
dt

The equation for a travelling wave in differential form can be written as,
d2y 1 d2y

dx 2 v 2 dt 2

Then by analogy, the wave equation for a de Broglie wave for the motion of a
free particle can be written as
 d 2 1 d 2
 2 ----------------- (6)
dx 2 v dt 2

This equation represents the waves propagating along x-axis with a velocity ‘v’,
and ‘x’ is the displacement at time ‘t’.
Substituting equations (4) and (5) in the above equation, we get
d 2
.( 2 e  t )
1
e-iωt . 
dx 2 2
v
d 2   2
 2 
dx 2 v

But, we know that  = 2ν and v = υ. Substituting for ω and v, we get
2
d2 ψ −4π2 ν −4π2
= ψ= ψ------- (7)
dx2 ν2 λ2 λ2
ℎ ℎ
But, we have, 𝜆 = = . Then eq.(7) becomes
𝑝 𝑚𝑣
2
d2 ψ 4π2 m2 ν
+ ψ = 0 -------------- (8)
dx2 h2

We know that,
Total Energy = Kinetic Energy + Potential Energy
E = KE +PE
𝑚𝑣 2
E= +𝑉
2

𝑚2 𝑣 2 = 2𝑚(𝐸 − 𝑉) ----------- (9)

Substitute eq. (9) in (8), then
d2 ψ 4π2 2𝑚(𝐸 − 𝑉)
+ ψ=0
dx 2 h2
𝐝𝟐 𝛙 𝟖𝛑𝟐 𝒎(𝑬 − 𝑽)
+ 𝛙=𝟎
𝐝𝐱 𝟐 𝐡𝟐

This is known as time independent Schrodinger wave equation in one

dimension.
𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝟖𝛑𝟐 𝒎(𝑬− 𝑽)
+ + + 𝛙 = 𝟎 (3dimension)
𝐝𝐱 𝟐 𝐝𝐲 𝟐 𝐝𝐳 𝟐 𝐡𝟐

Applications of Schrodinger’s Equation:

(1) Particle in one dimensional potential well of infinite height:

Consider a particle of mass ‘m’ moving inside a box along the X – direction
between two rigid walls A and B. The particle is free to move between the walls
of the box at x = o and x = a. The potential energy of the particle is considered to
be zero inside the box and infinity at all points outside the box. This means that

1. PE, V=0 for 0 < x < a

2. PE,V= for x  0 and x  a

The particle is always inside the box and therefore the probability of finding the
particle outside the box is zero. Therefore the wave function  is zero for x  0
and x  a.
The Schrodinger’s equation for a particle is given by
𝐝𝟐 𝛙 𝟖𝛑𝟐 𝒎(𝑬 − 𝑽)
+ 𝛙=𝟎
𝐝𝐱 𝟐 𝐡𝟐
Since, V = 0 inside the box between the walls, the above equation reduces to
d 2 8 2 mE
   0 ---------- (1)
dx 2 h2
8π2 𝑚𝐸
Take, = k 2 --------------- (1A)
h2

Then, equation (1) becomes

𝐝𝟐 𝛙
+ 𝐤 𝟐 𝛙 = 𝟎 … … … . . … . . (𝟐)
𝐝𝐱 𝟐

The general solution for equation (2) is of the form

 = A Sin kx + B Cos kx --------------- (3)
Where A and B are constants. The values of these constants can be evaluated by
applying the following boundary conditions.
The particle cannot penetrate the walls. Hence

(i)  = 0 at x = 0

 (3)  0 = A sin 0 + B cos 0

0=0+B B=0
  = A Sinkx ------------- (4)

Again, (ii)  = 0 at x = a

(3) 0 = A Sin ka

But A ≠ 0; because if A = 0, then the entire function will become zero.

Therefore, Sin ka = 0 = Sin nπ

Ka = n, n = 0, 1, 2, 3,…..
𝐧𝛑
𝐤 = --------------- (5)
𝐚

Equation (4) becomes

 n = A sin ( nπ ) x --------------- (6)

a

Substituting equation (5) in (1A), we get

n 2 π 2 8π 2 mE n
 
a2 h2

n 2h 2
 En = ------------------- (7)
8ma 2

Where n = 1, 2, 3…….
When n = 1 is the lowest energy level given by
h2
E1 =
8ma 2
This energy is called the zero-point energy. Also,
h2 4h 2 9h 2
E1 =  E0 E2 = E3 =
8ma 2 , 8ma 2 , 8ma 2 ……
For each value of ‘n’ there is an energy level. The possible allowed values of
energy obtained from equation (7) i.e., E1, E2, E3 etc. are called Eigen values and
the corresponding wave function n is called the Eigen function.

The energy corresponding to n = 1 is called ground state energy or zero point

energy and the energy levels for n = 2, 3, 4, 5… are called excited states.
Inside the well, the particles can have discrete set of values of energy and it is
quantized i.e.,
E2 = 4E0, E3 = 9E0, E4 = 16E0, and so on.
Normalization of wave function (evaluation of the value of A):

We have,
nπ
n = A sin ( )x
a
The constant A of this equation can be obtained by applying the normalization
condition i.e.,

a 2
∫0 |ψn | dx = 1

L nπk
∫0 A2 Sin2 a
xdx = 1
1−Cos2 2θ
We know that sin2 θ = .
2

Then
a A2 Cos2nπx
∫0 2
(1 − a
) dx = 1
a
a
A2 Cos2nπx
⟹ [∫(1)dx − ∫ dx] = 1
2 0 a
0
A2 A2 𝑎 Sin 2nπx 𝑎
⟹ [𝑥]𝑎 − [ ] =0
2 2 2𝑛𝜋 a
 𝑎
A2 a A2 a Sin 2nπa
⟹ − [ ] = 0 ⇒ Sin(2nπ) = 0
2 4nπ a

A2 a 2
= 1 ⇒ A = √ ……… (8)
2 a

2 nπx
ψn = √ sin
a a

The normalized wave function of the particle is

2 nπx
ψn = √ sin
a a

Wave functions, probability densities and energy Eigen values for a

particle in a box:
The first three energy levels (Eigen Values) E1, E2, E3 and their corresponding
wave function is  1, 2, 3 and probability densities corresponding to n = 1,2, &
3 respectively.

Case (1)
For n = 1, the Eigen function is
  1 = A sin   x
π
a
 1 is maximum at x = a/2.
Thus a plot of 1 versus x will be as shown in figure and a plot of probability
density 12 versus x is as shown in figure. The probability of finding the
particle is zero both at x = 0 and
x = a. It is maximum at x = a/2. This means that in the ground state, the
probability of finding the particle is maximum at the center of the box.
h2
Also, the ground state energy, E1 =  E0
8ma 2 .
Case (2)
At n=2, the Eigen function for the first excited state is
2π
2 = A sin x
a
2 = 0 at x = 0, a/2 and a.
2 is maximum at the positions x = a/4 and 3a/4.
The plot of 2 versus x and the probability density 22 versus x is as shown
in fig.
Since 22 = 0 at x = 0, a/2 and a, this means in the first excited state the particle
cannot be observed either at the walls or at the center.
4h 2
Here, the energy of the first excited state is E2 = = 4E0
8ma 2

Case (3)
At n=3; the second excited state, the Eigen function for the second excited state
is given by
3
3 = A sin x,
a
3 = 0 for x = 0, a/3, 2a/3 and a.
3 has maximum value for x = a/6, a/2 and 5a/6.
A plot of 3 versus x and probability density 32 versus x is as shown in fig.
For each value of n there is an energy level as obtained from equation (1).
9h 2
Here, E3 = = 9E0
8ma 2
Hence, the energy levels are discrete. Each energy value of En is called Energy
Eigen value. The Eigen value for the corresponding wave function  n is called
the Eigen function. The energy values that are permissible in any system are
obtained from the solution of the Schrodinger’s equation and are called Eigen
Value