Module-1

Modern Physics and Quantum mechanics

Introduction - Need of Modern Physics

Three important experimental discoveries namely black body spectrum, photoelectric effect
and Compton Effect initiated the need of new physics-Modern Physics. Modern Physics is the
Physics of 20th century. It is a branch of physics that deals with the post-Newtonian concepts
in the areas of physics. It led to the major breakthroughs of the twentieth century: theory of
Relativity and Quantum Mechanics.

Wave-Particle dualism

Wave-particle duality is the concept in quantum mechanics that every particle or quantum
entity may be described as either a particle or a wave. On the basis of experimental evidence,
Einstein first showed (1905) that light waves must also be considered as stream of particles.
Based on this Louis de-Broglie proposed (1924) that material particles such as electrons, atoms
molecules etc also behave as wave.

de-Broglie Hypothesis

de-Broglie hypothesis states that every moving material particle is associated with a wave and
this wave is called Matter wave or de-Broglie wave. The wave and particle properties are not
exhibited simultaneously.

The wavelength () of matter wave or de-Broglie wave is given by

ℎ
𝜆=
𝑝
It can be derived as follows
According to Einstein’s mass energy relation
𝐸 = 𝑚𝑐 2 − − − (1)
According to Planck’s quantum theory of radiation
𝐸 = ℎ𝜈 − − − (2)
From Eq (1) and Eq (2) we get
𝑚𝑐 2 = ℎ𝜈
ℎ𝜈
𝑚𝑐 =
𝑐
𝑐
Put 𝑚𝑐 = 𝑝 momentum and = 𝜆 wavelength
𝜈
ℎ
𝑝=
𝜆
ℎ
𝜆=
𝑝
This is the expression for wavelength. For a particle of mass m moving with velocity v we
can write
 ℎ
𝜆=
𝑚𝑣
This equation can be rewritten as
ℎ
𝜆=
√2𝑚(𝐾𝐸)
ℎ
𝜆=
√2𝑚𝑞𝑉
For a thermally accelerated particle
ℎ
𝜆=
√3𝑚𝑘𝑇

Characteristic properties of Matter waves

i. Mater waves are produced by moving particles. Hence they are neither electromagnetic
nor acoustic in nature
ii. They can travel in vacuum. Presence or absence of material medium does not affect
their behaviour
iii. Matter wave is associated with a periodic variable called wave function. It represents
the probability of finding the particle at given (x,t)
iv. The amplitude of a matter wave in a particular region represents the maximum
probability of finding the particle
v. The wavelength associated with a moving material particle is independent of its charge.
vi. Matter waves are associated with two velocities namely phase velocity (vph) and group
velocity (vg)
vii. Phase velocity is greater than speed of light. Hence it does not carry physical
significance
viii. The particle’s position, momentum and other parameters can be better explained by
matter waves associated with them. Hence matter waves are treated as “guiding waves”.

Phase velocity (vph) and group velocity (vg)

A progressive wave is given by

𝑦(𝑥, 𝑡) = 𝐴 sin(𝜔𝑡 − 𝑘𝑥 + 𝜙).
Here  is the phase term.
The velocity with which this wave propagate in an isotropic medium is known as phase
velocity. It is given by
𝜔
𝑣=
𝑘
It represents the velocity at which phase of any one frequency component of the wave
travels.
In the given wave A and B are two points on the wave separated by distance  and having
same phase of vibration and the time taken by the energy
reach B from A is T. Hence

𝜆 2𝜋/𝑘 𝝎
𝑣= = ⇒𝒗=
𝑇 2𝜋/𝜔 𝒌
A particle in motion is represented in the form of wave packet or wave group. This type of
wave group is formed when two or more waves of slightly different wavelength and frequency
superimpose (like in the case of beats). The velocity with which this wave group travels is
known as group velocity (vg).
d𝜔
𝑣𝑔 =
d𝑘
The following fig represent the superposition of two waves of slightly different frequency and
formation of a wave group. The wave group travels with group velocity

Significance of the Wave group

Wave group of matter waves represents the particle motion since its velocity is same as velocity
of the particle. It is a representative of moving particle. The particle can be located anywhere
within the group at a given time. The narrower its wave group, the more precisely particle
position can be specified. In the following figures, the position measurement is accurate in the
case of Fig.1 than in Fig.2. On the other hand wider wave group (Fig.2) has a clearly defined
wavelength. The momentum that corresponds to this wavelength is more accurate.

Fig-1 Fig-2

Principle of complementarity

One of the milestones of quantum mechanics is Bohr's complementarity principle. It states that
a single quantum can exhibit a particle-like or a wave-like behaviour, but never both at the
same time. This means that we need distinct experimental arrangements in order to measure
the particle or the wave nature of a physical system.
When importance is given to the particle nature its wave nature is suppressed and vice versa.
The inability to observe the wave nature and the particle nature of the matter simultaneously
is known as the complementarity principle.

Heisenberg uncertainty principle

The uncertainty principle states that

In the simultaneous measurements of both position and momentum of a particle, there is always
some error. The product of error in the position and momentum is greater than or equal to
(h/4).
If x is the error in position and p is that in momentum then
ℎ
Δ𝑥Δ𝑝 ≥
4𝜋
Uncertainty principle is also expressed in terms of energy (E) and time interval (t) as
ℎ
Δ𝐸Δ𝑡 ≥
4𝜋

If the width of the wave group (x) is small then position measurement is accurate but not the
momentum. If we reduce p somehow, a broader wave group is inevitable and hence x is
large. These uncertainties are not due to inadequate apparatus but to the imprecise character in
nature of the quantities involved.

Impossibility of existence of electrons inside the atomic nucleus

It is well known that electrons do not exist inside the atomic nucleus. The same can be shown
by using Heisenberg uncertainty principle as follows.

Let us make an assumption that electrons exist inside the atomic nucleus. We know that the
size of nucleus is of the order of 10fm = 10x10-15m. For an electron to exist inside the
nucleus, uncertainty in its position x must not exceed size of the nucleus.
i.e x  10x10-15m
i.e x is less than or equal to 10x10-15m.
By Heisenberg uncertainty principle we know that
h
x . p x  ----- (1)
4
Therefore, uncertainty in the measurement of momentum of electron inside the nucleus is
h
p x  ---- (2)
4  . x
Allowing maximum uncertainty for the position of electron i.e x = 10x10-15m, we get
6.63𝑥10−34
𝛥𝑝𝑥 ≥
4𝜋𝑥10𝑥10−15

i.e. 𝛥𝑝𝑥 ≥ 0.5𝑥10−20 𝑘𝑔𝑚𝑠 −1 ---- (3)

Therefore, uncertainty in the momentum of electron is equal to or greater than
0.5𝑥10−20 𝑘𝑔𝑚𝑠 −1. But, the momentum of the electron p x must be at least equal to or
greater than the order of uncertainty in momentum.
i.e. 𝑝𝑥 ≥ 0.5𝑥10−20 𝑘𝑔𝑚𝑠 −1 ------- (4)
But, we know that the non-relativistic expression for energy in terms of its momentum p x is

𝐸 = 𝑝𝑥2 /2𝑚 ----------(5)

where m = 9.1x10-31kg is the rest mass of electron.

By using equation (4) in equation (5), we may conclude that, if an electron exist inside the
atomic nucleus, its energy ‘E’ must be such that
𝐸 ≥ 𝑝𝑥2 /2𝑚
𝐸 ≥ (0.5𝑥10−20 )2 /(2𝑥9.1𝑥10−31 )
𝐸 ≥ 1.372𝑥10−11 𝐽
𝐸 ≥ 85𝑀𝑒𝑉
It means for an electron to exist inside the atomic nucleus its energy must be greater than or
equal to 85MeV. But, electrons emitted from nucleus in -decay experiment have energies in
the range of 3 – 4 MeV. This discrepancy with respect to energy of electron indicates that
electrons do not exist inside the nucleus.

Physical significance of Heisenberg uncertainty principle

The physical significance of Heisenberg uncertainty principle is that, one should not think of
the exact position or an accurate value for momentum of a particle. Instead, one should think
of probability of finding the particle at a certain position or the most probable value for
momentum of the particle. This principle confirms the wave nature of matter.

Quantum Mechanics
Introduction

In Classical Mechanics (or Newtonian Mechanics) the future history of the particle is
completely determined by its initial position and momentum together with the forces that act
upon it. In everyday life these measurements holds good satisfactorily. However, because of
uncertainty principle, nature of an observable quantity is different in atomic and subatomic
world. This initiates a new approach called “Quantum Mechanics”.

Wave function (ψ)

Wave function is the mathematical function in quantum mechanics which is determined by

the physical situation of the system and, it is the function of coordinates of a particle in space
i.e x, y, z and t. It is represented by the symbol ψ.
Wave function ψ also contain all the possible information about the system. Hence it is also
called as state function. Such wave functions are obtained by solving Schrodinger wave
equation.
Like Newton’s second law of motion is fundamental equation of Newtonian mechanics,
Schrodinger’s equation is for quantum.
Schrodinger 1-d time independent wave equation:
A progressive wave propagating along x-axis can be represented in the form of 2nd order
differential equation as follows.
𝑑2𝑦 1 𝑑2 𝑦
=
𝑑𝑥 2 𝑣 2 𝑑𝑡 2
Where y is f(x,t). Similarly a wave equation for a matter wave can be represented as
𝑑2𝜓 1 𝑑2 𝜓
= − − − − − (1)
𝑑𝑥 2 𝑣 2 𝑑𝑡 2
The solution for this equation is

𝜓 = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) where the symbols have their usual meanings.

𝑑𝜓
= 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) (−𝑖𝜔)
𝑑𝑡
𝑑2𝜓
= 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) (−𝑖𝜔)2 = −𝜔2 𝜓
𝑑𝑡 2
Hence equation (1) becomes
𝑑2𝜓 1
= (−𝜔2 𝜓)
𝑑𝑥 2 𝜔 2
( )
𝑘
𝑑2𝜓 2
−4𝜋 2
= (−𝑘 𝜓) = 𝜓
𝑑𝑥 2 𝜆2
𝑑2𝜓 1
2
= (−4𝜋 2 𝜓) 2 − − − − − − (2)
𝑑𝑥 𝜆
The total energy of a particle is
E = KE + PE  KE = E – PE = (E – V)
But
ℎ ℎ2
𝜆= ⇒ 𝜆2 =
√2𝑚(𝐾𝐸) 2𝑚(𝐾𝐸)

ℎ2
𝜆2 =
2𝑚(𝐸 − 𝑉)
1 2𝑚
∴ = (𝐸 − 𝑉) − − − − − −(3)
𝜆2 ℎ2
Substitute (3) in (2)
𝑑2𝜓 2𝑚
2
= (−4𝜋 2 𝜓) 2 (𝐸 − 𝑉)
𝑑𝑥 ℎ
𝒅𝟐 𝝍 𝟖𝝅𝟐 𝒎
+ (𝑬 − 𝑽)𝝍 = 𝟎
𝒅𝒙𝟐 𝒉𝟐
This is 1-d time independent Schrodinger wave equation. In 3-d
𝑑 2 𝜓 𝑑 2 𝜓 𝑑2 𝜓 8𝜋 2 𝑚
+ + + (𝐸 − 𝑉)𝜓 = 0
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2 ℎ2

2
8𝜋 2 𝑚
∇ 𝜓+ (𝐸 − 𝑉)𝜓 = 0
ℎ2
Characteristics of wave function:
There can be many solutions to the Schrodinger wave equation but only wave functions with
following properties must be considered as “well behaved” or “proper” wave functions. Only
they can give physically meaningful results when used in calculations. The properties are
i.  must be continuous and single valued everywhere.
𝜕𝜓 𝜕𝜓
ii. and must be continuous and single valued everywhere.
𝜕𝑥 𝜕𝑡
iii.  must be normalizable and it should not be .

Wave function possessing all these properties is known as eigen function and the energy value
obtained by solving Schrodinger wave equation using eigen function is known as eigen value.

Physical significance of wave function (Max Born Approximation)

The wave function itself does not have direct physical meaning. It only represents the
probability of finding a body (or particle) at a given place and at a given time. It must lie
between 0 and 1 and the maximum probability is analogous to amplitude of an ordinary wave.
Amplitude of a wave can be positive as well as negative but negative probability is
meaningless. In order to overcome this problem Max Born gave an approximation (called
Born’s approximation) as follows.
The probability of finding a particle described by the wave function  at a point x and at time
t is proportional to probability density |𝜓2 | at (x,t).
Probability density is equivalent to radiation density or intensity (I=A2). Even though  can
be imaginary, positive or negative |𝜓2 | is always positive. Hence the probability density is
more significant than probability alone. It is obtained by multiplying the wave function by its
complex conjugate.
∴ |𝜓2 | = 𝜓 ∗ 𝜓
Normalization:
Consider a particle enclosed in 3-dimenstional contour of volume V. Its probability density
(probability of finding the particle) over a small volume dV is |𝜓2 |𝑑𝑉. If make several attempts
to find the particle over the entire volume, then obviously integral (or total) cannot be ZERO
or INFINTY. The only possibility is, it is equal to ONE.
𝑉
∫ |𝜓2 |𝑑𝑉 = 1
0

The wave function that obeys this equation is said to be normalized and the whole process is
known as Normalization.
Normalization in 1-dimension is
𝑥
∫ |𝜓2 |𝑑𝑥 = 1
0

And normalization for a particle in space is

 ∞
∫ |𝜓2 |𝑑𝑥 = 1
−∞

Application of Schrodinger wave equation:

Particle in 1-D potential well (Infinite height):
This is the simplest quantum mechanical problem taken to explain the application of
Schrodinger wave equation. In this model a quantum particle (say electron) is assumed to be
trapped in a 1- dimensional potential well of infinite height and width of a. its walls are
extremely hard so that the collision between wall and particle is perfectly elastic. The potential
energy of the particle is zero inside and infinity outside the well. Particle is restricted to move
only along x-axis (i,e from x = 0 to x = a). The boundary conditions are as follows.
i. 𝜓 = 0 and 𝑉 = ∞ outside the well.
ii. 𝜓 ≠ 0 and 𝑉 = 0 for 0 < 𝑥 < 𝑎 (inside the well).
iii. 𝜓 = 0 for 𝑥 ≤ 0 and 𝑥 ≥ 𝑎.

Case-1:
Outside the well, V = . Hence Schrodinger wave equation
𝑑 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 𝑉)𝜓 = 0 (1)
𝑑𝑥 2 ℎ2
becomes
𝑑 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − ∞)𝜓 = 0
𝑑𝑥 2 ℎ2
The possible solution for this equation is  = 0. This means that the probability of finding the
particle and hence probability density outside the well is ZERO.
Case-2:
Inside the well, V = 0 and hence equation (1) becomes
𝑑 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 0)𝜓 = 0
𝑑𝑥 2 ℎ2
Even though  = 0 is a possible solution it cannot be considered for obvious reason.
Put
2
8𝜋 2 𝑚𝐸
𝑘 = (2)
ℎ2
𝑑2𝜓
+ 𝑘2𝜓 = 0
𝑑𝑥 2
This is a second order differential equation and its solution is
𝜓 = 𝐶 cos 𝑘𝑥 + 𝐷 sin 𝑘𝑥 (3)
Put x = 0 and  = 0, we get
C = 0.
Again, put x = a and  = 0, we get
0 = 0 cos 𝑘𝑎 + 𝐷 sin 𝑘𝑎
𝐷 sin 𝑘𝑎 = 0 ⟹ 𝐷 ≠ 0 and sin 𝑘𝑎 = 0
∴ 𝑘𝑎 = 𝑠𝑖𝑛−1 (0) ⟹ 𝑘𝑎 = 𝑛𝜋
𝑛𝜋
∴𝑘= (4)
𝑎
Here n = 1,2,3,4…
From equation (2) and (3) we get
8𝜋 2 𝑚𝐸 𝑛𝜋 2
= ( )
ℎ2 𝑎
𝑛2 ℎ2
𝐸=
8𝑚𝑎2
Or,
𝒏𝟐 𝒉𝟐
𝑬𝒏 =
𝟖𝒎𝒂𝟐
If n =1, then we get ground state energy of the particle. It is also called as ZERO POINT energy.
𝒉𝟐
𝑬𝒁𝑬𝑹𝑶 =
𝟖𝒎𝒂𝟐
Substitute C and k in equation (3) we get
𝑛𝜋
𝜓𝑛 = 𝐷 sin 𝑥 (5)
𝑎
Normalization (To find D):
Consider
𝑎
∫ |𝜓2 𝑛 |𝑑𝑥 = 1
0
𝑎
𝑛𝜋 2
∫ (𝐷 sin 𝑥) 𝑑𝑥 = 1
0 𝑎
𝑎
𝑛𝜋𝑥
∫ 𝐷2 sin2 𝑑𝑥 = 1
0 𝑎

𝐷2 𝑎 2𝑛𝜋𝑥
∫ (1 − 𝑐𝑜𝑠 ) 𝑑𝑥 = 1 because 𝑠𝑖𝑛2 𝜃 = (1 − 𝑐𝑜𝑠2𝜃)/2
2 0 𝑎

𝐷2 𝑎 𝑎
2𝑛𝜋𝑥
[∫ 𝑑𝑥 − ∫ 𝑐𝑜𝑠 𝑑𝑥] = 1
2 0 0 𝑎

𝐷2 𝑎 2𝑛𝜋𝑎
[(𝑎 − 0) − (𝑠𝑖𝑛 − sin 0)] = 1
2 2𝑛𝜋 𝑎
𝐷2 𝑎
[𝑎 − (sin 2𝑛𝜋 − sin 0] = 1
2 2𝑛𝜋
𝐷2 𝑎
[𝑎 − (0 − 0)] = 1
2 2𝑛𝜋
𝐷2
𝑎=1
2

2
𝐷=√
𝑎

Hence equation (5) becomes

𝒏𝝅
𝝍𝒏 = √𝟐/𝒂 𝐬𝐢𝐧( )𝒙
𝒂
This is the eigen function.
Eigen functions, energy eigen values and probability densities for a particle in a box:
Consider a particle present in 1-dimentional potential well of infinite height and finite width a.
its eigen function and eigen value, in general, are given by
𝑛𝜋
𝜓𝑛 = √2/𝑎 sin( )𝑥
𝑎
and
𝑛2 ℎ2
𝐸𝑛 =
8𝑚𝑎2
Case-1:
Put n =1, then we get ground state energy as
ℎ2
𝐸0 =
8𝑚𝑎2
The eigen function becomes
𝜋
𝜓1 = √2/𝑎 sin(𝑎 )𝑥
1 12
(i) Put x =0, 𝜓1 = 0 and

|𝜓12 | = 0
𝜋
2 ( )𝑎 2
𝑎
(ii) Put x =a/2, 𝜓1 = √𝑎 sin = √𝑎 and
2

|𝜓12 | = 2/𝑎
(iii)Put x =a, 𝜓1 = 0 and

|𝜓12 | = 0
Case-2:
Put n =2, we get 𝐸1 = 4𝐸0
The eigen function becomes
2𝜋
𝜓2 = √2/𝑎 sin( )𝑥
𝑎
(i) Put x=0, 𝜓2 = 0 |𝜓22 | = 0

2𝜋
2 ( )𝑎 2
(ii) Put x=a/4, 𝜓2 = √𝑎 sin 𝑎
= √𝑎 |𝜓22 | = 2/𝑎
4

(iii)Put x=a/2, 𝜓2 = 0 |𝜓22 | = 0

2𝜋
2 ( )3𝑎 2
(iv) Put x=3a/4, 𝜓2 = √𝑎 sin 𝑎
= − √𝑎 |𝜓22 | = 2/𝑎
4

(v) Put x=a, 𝜓2 = 0 |𝜓22 | = 0

Similarly if n =3, 𝐸2 = 9𝐸0 and

3𝜋
𝜓3 = √2/𝑎 sin( )𝑥
𝑎
The graphical representation of 3 and 32 is as follows.

a/2

a/6 5a/6

3 32
The Eigen functions ψ’s together with probability densities ψ2’s for first three states (n=1, 2,
3) are plotted in figure below.
Energy Eigen values
n 2h 2
From Equation (10) we have the Energy Eigen value as E 
8ma 2
h2
For n = 1 (Ground state energy or zero point energy), E1 
8ma 2
4h 2
For n = 2 (First excited state energy), E 2   4E1
8ma 2
9h 2
For n = 3 (Second excited state energy), E 3   9E1 etc.
8ma 2
From above equations it is clear that E1:E2:E3:……..=1:4:9:…….. It means that energy levels
are not equally spaced as shown in figure.
 Review questions

1. State and explain de-Broglie hypothesis.

2. Obtain the expression for de-Broglie wavelength in terms of mass and velocity.
3. State and explain Heisenberg uncertainty principle. Mention its physical significance.
4. Define the terms phase velocity and group velocity. Discuss the importance of wave group
5. What are the characteristics of matter waves
6. Write an explanatory note on principle of complementarity
7. State and explain Heisenberg uncertainty principle. What is its significance?
8. Show that electrons do not exist inside the nucleus based on Heisenberg uncertainty principle.
9. State and explain Heisenberg Uncertainty principle. Show that the electron emitted during β
decay does not pre-exist inside the nucleus using uncertainty principle.
10. What are the properties of a wave function? Give the qualitative explanation of Max Born’s
interpretation of wave function.
11. Setup 1-dimensional time independent Schrodinger wave equation. Explain Born’s
interpretation of wave function.
12. Define Wave function, Eigen function and Eigen value.
13. Staring from Schrodinger’s time independent wave equation, derive the expression for energy
eigen value and eigen function for an electron present in 1-d potential well of infinite depth.

Exercise Problems:
1. Calculate the de-Broglie wavelength of a macroscopic particle of mass 0.5kg moving with a
speed of 150km per hour and a microscopic particle of mass 9.1x10-31 kg moving with a speed
of 1x106ms-1.
2. Calculate the de-Broglie wavelengths of proton, electron and α-particle when they are
accelerated by potentials of 100V, 200V and 300V respectively.
3. Calculate the potential through which an electron needs to be accelerated so that its de-Broglie
wavelength becomes equal to 1Å.
4. Compare the momentum and total energy of electron and photon when both are associated with
a wavelength of 2nm.
5. The position and momentum of an electron are simultaneously determined. If its position is
located within 0.5 Å find the uncertainty in the determination of its momentum.
6. The position and momentum of an electron with energy 2keV are determined. If the inherent
uncertainty in the measurement of its position is 0.25Å, what is the minimum percentage
uncertainty in its momentum.
7. The inherent uncertainty in the measurement of time spent by a nuclei in the excited state is
found to be 2x10-14s. Estimate the uncertainty that results in its energy in the excited state.
(Answer: ΔE = 0.016eV)
8. A spectral line of wavelength 5461 Å has a width of 10-4 Å. Evaluate the minimum time spent
by the electrons in the upper energy state.
9. An electron is confined to move between two rigid walls separated by 20 Å. Find the de-Broglie
wavelength representing the first three allowed energy states of the electron and the
corresponding energies.
10. Calculate the zero point energy for an electron in a box of width 10 Å.
11. Find the energy spacing between first and third excited states of an electron confined to a
potential well of infinite height and finite width of 1 Å.
12. Find the normalization constant if an electron moves in an one dimensional box of length 2
nm.
13. A quantum particle confined to one dimensional box of width ‘a’ is in its first excited state.
What is the probability of finding the particle over an interval of (a/2) marked symmetrically
at the center of the box.
14. A particle moving in one dimensional box is described by the wave function
𝜓 = 𝑥[√3] 𝑓𝑜𝑟 𝑥 < 𝑥 < 1 and ψ = 0 elsewhere
Find the probability of finding the particle within the interval (0, ½)