Physics (BPH-151/152)

Dr. Alok Singh

School of Basic & Applied Sciences

Department of Physics
Harcourt Butler Technical University, Kanpur
B.Tech. First Year Course
 Module 2:
Quantum Mechanics
 Why Relativity?

electrons, protons, Neutrons

 Dual Nature of Matter & Radiation
➢ In optical phenomena such as interference, diffraction
and polarization light shows its wave nature. These
phenomena can be explained by wave theory of light.
➢ But, the wave theory of light is failed to explain photo
electric effect, Compton effect, absorption and
emission of radiation. These phenomena are explained
by quantum theory of light. Einstein explains that the
energy of light is concentrated into small regions
known as photon or energy particle.
➢ Thus in some experiment light behave like a wave and
in some other experiment light behave like a particle.
➢ This is known as dual nature of light and the property
of this dual nature is known as wave particle duality.
De- Broglie’s Hypothesis of Matter Waves:
❖A moving microscopic particle behaves as wave.
According to De-Broglie hypothesis “A moving
microscopic particle is associated with a wave
known as De- Broglie wave or matter wave”. The
wavelength of De-Broglie waves are given by,

Where, h = Plank’s constant (6.63x10-34 J.s)

m = Mass of the particle
v = velocity of the particle
 The expression for the wavelength of De-Broglie
waves:
According to the Planck’s theory of radiation, the energy of photon’s
are given by,

According to the Einstein’s mass energy relation,

𝐸 = 𝑚𝐶 2
On substituting the value of E in equation (1), we get,

Where, mC is the momentum of photons. If a particle of mass m

moves with the velocity v, then the De-Broglie wavelength is given
by,
De-Broglie wavelength for a free particle in terms
of its kinetic energy:
1) If a particle has kinetic energy E, moves with the
velocity v having mass m then,

𝑃 = 2𝑚𝐸
Therefore, the De-Broglie wave is given by,
 De-Broglie wavelength for a free particle in terms
of its kinetic energy:
2) If q is the charge of the particle which is accelerated by a
potential difference of V volts then, it’s kinetic energy is given by,
𝐸 = 𝑞𝑉
Therefore, the De-Broglie wavelength is given by,

3) If a material particle is in thermal equilibrium at temperature T,

then the kinetic energy is given by,

Where, k = Boltzmann constant (1.38x 10-23 J/K)

Therefore, the De-Broglie wavelength is given by,
 De-Broglie wavelength for a free particle in terms
of its kinetic energy:
4) If a particle moves with high velocity which is comparable to the
velocity of light then, the mass of the particle is given by,
𝑚0
𝑚=
𝑣2
1− 2
𝐶

Therefore, the De-Broglie wavelength is given by,

5) If an electron is accelerated by a potential of V volts, then, the De-

Broglie wavelength is given by,
 Properties of Matter Waves:

❑The properties of matter waves or De-Broglie’s are

as follows,
➢Lighter is the particle, longer will be the De-
Broglie’s wavelength.
➢If the velocity will smaller then, the De-Broglie’s
wavelength will be larger.
➢When V=0 the 𝜆 = ∞ , this is indeterminate case.
Thus, De-Broglie’s wavelength is associated with
a moving particle only. They are not
electromagnetic waves but they are a new kind of
waves.
Ex. 1: Find the de-Broglie wavelength of a 15 keV electron.
Sol.: The kinetic energy of an electron is,

where, 𝑚0 = 9.1 × 10−31 𝑘𝑔 is the mass of an electron and v is

its velocity,

The momentum of an electron, p = m0v = 9.1x10-31x103 kgm/s

p = 9.1x10-28 kgm/s
According to the de-Broglie's concept of matter wave,
Ex.2: Calculate the velocity and kinetic energy of a neutron
having de-Broglie wavelength 1Ǻ.
Sol.: According to the de-Broglie's concept of matter wave,

Here, ℎ = 6.62 × 10−34 𝐽 − 𝑠𝑒𝑐, 𝑚 = 1.67 × 10−27 𝐾𝑔 and

𝜆 = 1Å = 10−10 𝑚

The kinetic energy of the neutron is,

= 1.309 × 10−20 𝑗𝑜𝑢𝑙𝑒

1.309×10−20
or 𝐸 = 1.6×10−19
= 0.082𝑒𝑉
Ex.3: A proton is moving with a speed of 2x108 m/s. Find the
wavelength of the matter wave associated with it.
Sol.: The wavelength of matter wave associated with a particle is,

𝑚0 𝑣
The momentum, 𝑝 = 𝑚𝑣 =
𝑣2
1− 2
𝑐
Here, the rest mass of proton, 𝑚0 = 1.67 × 10−27 𝑘𝑔, 𝑣 = 2 ×
108 𝑚/𝑠,
 Wave Packet or Wave group:
❑A moving microscopic particle is not equivalent
to a single wave but it is equivalent to a group of
waves or wave group.
❑A wave packet is constructed by a bunch of waves
which slightly differs in velocity and propagation
constant. The phase of these waves is such that
they interfere in the space to produce a resulting
wave with the varying envelope. Therefore, a
wave packet has a beginning and an end as shown
in figure below.
Wave Packet or Wave group:
Group Velocity and Phase Velocity
➢“The velocity with which the wave packet
moves known as group velocity and it is
represented by vg”.
or
➢“The average velocity of the individual
monochromatic wave with which a wave
packet is constructed is known as phase
velocity or wave velocity and it is denoted by
vp”.
 Velocity of De-Broglie waves:
According to De-Broglie wavelength,

According to the Plank’s theory of radiation, the energy of a photon is

given by,
𝐸
𝐸 = ℎ𝜈 ⟹ 𝜈 = 2
ℎ
The velocity of De-Broglie waves is given by,
𝑣𝑝 = 𝜈𝜆

𝐸
𝑣𝑝 = [𝑆𝑖𝑛𝑐𝑒 𝐸 = 𝑚𝐶2 ]
𝑚𝑣
➢According to the above expression the velocity of
the particle v is always less than velocity of light C.
➢Therefore, vp > C, which is not possible according
to the relativistic mass variation with velocity.
➢This contradiction was resolved by Schrödinger by
postulating that a material particle is not equivalent
to a single wave train. But it is equivalent to a
group of wave or wave group.
 Relation between group velocity and phase
velocity:
We know that the phase velocity is given by,

Since, we have a relation,

Ex.3: An electron has de-Broglie wavelength 2.0x10-12 m. Find its kinetic energy. Also find the
phase and group velocity of its de-Broglie waves.
Sol.: Since the electron has very small wavelength, relativistic correction should be applied. The
relativistic mass m of an electron is,

where, E is the total energy and E0 is the rest energy of moving electron.
Total energy E of the electron is given by,
𝐸 = 𝑝𝑐 2 + 𝑚0 𝑐 2 2
ℎ𝑐 6.63 × 10−34 × 3 × 108
𝑝𝑐 = = = 621.56 𝑘𝑒𝑉
𝜆 2 × 10−12 × 1.6 × 10−19
2 9.1 × 10−31 × (3 × 108 )2
𝑚0𝑐 = = 511 𝑘𝑒𝑉
1.6 × 10−19
Thus, the kinetic energy of the electron 𝐾 = 𝐸 − 𝑚0𝑐 2 = 804.64 − 511 = 293.64 𝑘𝑒𝑉,

Thus, the group velocity of the de-Broglie waves, 𝑣𝑔 = 𝑣 = 0.7724𝑐

𝑐2
The phase velocity of the de-Broglie waves, 𝑣𝑝 = 𝑣 = 1.29𝑐
𝑔
On substituting the value of w from eq.(1),

This is the relation between group velocity and phase velocity in

dispersive medium.
(When wave velocity is dependent on frequency than the medium is
known as dispersive medium)
For non dispersive medium that is wave velocity is independent of
frequency than,

𝑣𝑔 = 𝑣𝑝
For non dispersive medium group velocity is equal to phase
velocity.
Relation between Group velocity and Particle
velocity:
We know that group velocity is given by,

2𝜋𝐸
Since, 𝜔 = 2𝜋𝜈 ⟹ ∵ 𝐸 = ℎ𝜈
ℎ
On differentiating the above eq. w.r.t. v, we get,

Since, the propagation vector is given by,

On differentiating the above eq. w.r.t. v, we get,
On substituting the values of eq. (3) and (4)
in eq. (1),

𝑣𝑔 = 𝑣
Thus, the velocity of microscopic particle is equal to
the velocity of wave packet or particle velocity, i.e.,
the particle must be located inside the wave packet.
 Davisson and Germer Experiment:

➢The first evidence that the stream of material

particle show wave like properties was given by
Davisson and Germer experiment in 1927 during
his diffraction experiment with slow electrons.
➢“The Davisson Germer experiment confirms the
existence of wave associated with electrons by
detecting De-Broglie waves but also succeeded in
measuring their wavelength”.
Figure1: Schematic of Davisson Germer Experimental Setup.
 Details of Experimental setup:
The Davisson and Germer apparatus is shown in figure 1.
Electrons from the heated filament are accelerated
through a variable potential ‘V’ and emerge from the
electron gun ‘G’. The electron beam falls normally on a
Nickel single target crystal. The electrons are diffracted or
scattered from the crystal in all direction because the
Nickel single target crystal acts as a three dimensional
diffraction grating i.e., the spacing between two
consecutive Nickel atoms considered as slit width. The
intensity of diffracted or scattered beam of electrons in
different directions is measured by a Faraday cylinder
(Detector) which is connected to a galvanometer ‘G’ and
can move on a circular scale. The whole apparatus is
enclosed in an evacuated chamber.
➢The current which is the measure of intensity of
diffracted beam or diffracted electron beam is
plotted against the diffraction angle φ for each
accelerating potential as shown in figure below.

Figure . Intensity of diffracted beam plotted against the diffraction angle φ for each
accelerating potential.
From the above curves as the potential difference is
increased the bump starts shifting upward and
become most prominent. The bump is most
significant for 54 V accelerating potential and at
diffraction angle 500. Beyond 54V the bump
gradually diminishes and become insignificant.
Thus, this is an evidence that electron were
diffracted by a target and verified the existence of an
electron wave.
 Calculations of the wavelength:

➢The corresponding angle of incidence is relative to

the family of Bragg’s planes is given by,

Figure 5. The corresponding angle of incidence in target plate.

According to the Bragg’s equation for the maxima, we have,
2𝑑 sin 𝜃 = 𝑛𝜆
Where, n = 1, d = 0.091 nm and 𝜃 = 650 , on substituting
these values we get,
𝜆 = 1.65 Å (1)
According to the De-Broglie’s wavelength for an electron,
we have,

𝜆 = 1.67 Å
Thus, from eq. (1) and eq. (2), it is clear that De-Broglie
wavelength of an electron wave by hypothesis and
experiment are almost same. Therefore, De-Broglie
hypothesis is verified by Davisson Germer experiment.
Heisenberg’s Uncertainty Principle:
Heisenberg states that," It is not possible to measure simultaneously
both the position and momentum (or velocity) of a microscopic
particle with an absolute accuracy or certainty”.
Mathematically it is expressed as,
ℎ
∆𝑥 × ∆𝑝 ≥ 1
4𝜋
Where, ∆𝑥 is Uncertainty in position ∆𝑝 is Uncertainty in momentum and
h is a Plank’s constant.
We know that,
𝑃 = 𝑚𝑣
∆𝑃 = 𝑚∆𝑣
ℎ
∆𝑥 × 𝑚∆𝑣 ≥
4𝜋
ℎ
∆𝑥 × ∆𝑣 ≥ (2)
4𝜋𝑚
So, the position of an electron or any microscopic particle and its velocity
cannot be measured simultaneously with accuracy.
 Derivation of Energy time Uncertainty relation from
Position Momentum Uncertainty Relation:
We know that,
ℎ
∆𝑥 × ∆𝑝 ≥
4𝜋
ℏ ℎ
Or, ∆𝑥 × ∆𝑝 ≥ (1) [∵ ℏ = ]
𝟐 2𝜋
If E is the kinetic energy of a free moving particle then, we know the relation,
1 𝑃 2
𝐸 = 𝑚𝑣 2 =
2 2𝑚
2𝑃∆𝑃
∆𝐸 =
2𝑚
𝑃∆𝑃 𝑚𝑣 ∆𝑃
∆𝐸 = =
𝑚 𝑚
∆𝑥 ∆𝑥
∆𝐸 = 𝑣 × ∆𝑃 = × ∆𝑃 ∵𝑣=
∆𝑡 ∆𝑡
∆𝐸 × ∆𝑡 = ∆𝑥 × ∆𝑃
From, eq.(1) we can write,
ℏ
∆𝐸 × ∆𝑡 ≥
𝟐
 Derivation of Heisenberg’s Uncertainty Principle:
The relationship between the distance ∆𝑥 and the wave number spread ∆𝑘 depends
upon the shape of the wave group. The minimum value of product ∆𝑥 × ∆𝑘 occurs
when the envelope of the group has a familiar bell shape of Gaussian function. If ∆𝑥
and ∆𝑘 are taken as the standard deviations of the respective functions 𝜓 (𝑥) and 𝑔 (𝑥),
1
the minimum value of product is ∆𝑥 × ∆𝑘 = . Since, wave groups in general do not
2
have Gaussian form; it is more realistic to express the relationship between ∆𝑥 and ∆𝑘
as,
1
∆𝑥∆𝑘 ≥ (1)
2
The De-Broglie wavelength of a particle of momentum p is 𝜆 = ℎ/𝑝 and the
corresponding wave number is,
2𝜋 2𝜋𝑝
𝑘= =
𝜆 ℎ
Hence, an uncertainty ∆𝑘 in the wave number of the De-Broglie waves associated with
the particle results in an uncertainty ∆𝑝 in the particle’s momentum then,
2𝜋∆𝑝
∆𝑘 = (2)
ℎ
On substituting the value of ∆𝑘 from eq. (2) to eq. (1) we get,
2𝜋∆𝑝 1
∆𝑥 × ≥
ℎ 2
ℎ
or, ∆𝑥 × ∆𝑝 ≥ (3)
4𝜋
Thus, the above expression is a Heisenberg’s uncertainty relation.
 Applications of Heisenberg’s Uncertainty Principle:
➢ Non-existence of electrons inside an atomic nucleus:
On the basis of Heisenberg’s uncertainty principle, it can be shown
that electron cannot exist (reside) inside the nucleus. The radius of
the atomic nucleus is of the order of 10-15 m. Therefore, Δx =
10-15 m, then the velocity of electron is given by,

∆𝑣 ≥ 5.77 × 1010 𝑚/𝑠

Thus, the value of uncertainty in velocity of an electron is very
high, i.e., it is greater than velocity of light which is not possible by
relativistic mechanics therefore electron cannot exist inside the
nucleus.
 The radius of Bohr's Orbit:
If ∆𝑝 and ∆𝑥 are the uncertainty in the momentum and position of an electron in the
orbit then,
𝒉 𝒉
∆𝑥 × ∆𝑝 ≥ ℏ ∵ = =ℏ
𝟒𝝅 𝟐𝝅
ℏ
∆𝑝 ≥ (1)
∆𝑥
The Kinetic energy of an electron can be written as,
∆𝑝 2
∆𝐾 =
2𝑚
𝟐
ℏ
∆𝐾 = (2)
2𝑚(∆𝑥)2
The potential energy of an electron can be written as,
𝑍𝑒 2
𝑉=−
𝑥
𝑍𝑒 2
∆𝑉 = −
∆𝑥
So, the uncertainty in the total energy of an electron is given as,
ℏ𝟐 𝑍𝑒 2
∆𝐸 = 2
− (3)
2𝑚(∆𝑥) ∆𝑥
The uncertainty in the energy will be minimum if,

On differentiating equation (3), we get,

Therefore, the radius of Bohr's first orbit is given by,

This is an expression for the radius of Bohr's first orbit.

 Binding energy of an electron in an atom:
Each atom consists of an electron moving in certain definite orbit
around a positively charged nucleus. The uncertainty in position ∆𝑥
of an electron is of the order of 2a, where, a is the radius of an orbit.
The corresponding uncertainty in the momentum is given by,

The non relativistic kinetic energy of an electron is given as,

The potential energy in the electrostatic field of the nucleus with

atomic weight Z is given by,
Thus, the total energy of an electron in the orbit is given by,
𝐸 =𝐾 +𝑉

On taking the radius of the orbit 𝑎 ≈ 10−10𝑚 , we have,

𝐸 = 1 − 15𝑍 𝑒𝑉
For hydrogen atom, i.e., Z=1,
𝐸 = −14 𝑒𝑉 ≈ −13.6 𝑒𝑉
It is well known that the binding energies of outermost electron
in hydrogen is -13.6 eV. It is same as obtained by above
expression. Hence, the binding energy derived from uncertainty
principle are comparable with magnitudes.
Ex.4: Calculate the uncertainty in the velocity of an
electron which is confined in a 10 Ǻ box.
Sol.: According to the Heisenberg uncertainty
principle,

uncertainty in velocity or ,
Here, mass of the electron 𝑚 = 9.1 × 10−31 𝑘𝑔
Ex. 5: An electron has a speed of 5x103 m/s within the
accuracy of 0.003%. Calculate the uncertainty in the
position of the electron.
Sol.: According to the Heisenberg uncertainty principle,
∆x∆p ≥ ℏ
The momentum of the electron, 𝑝 = 𝑚𝑣 = 9.0 ×
10−31 × 5 × 103 = 4.5 × 10−27 kgm/s
The uncertainty in the value of p is 0.003% of this value,
that is,

Therefore, the uncertainty in the position of this electron

is,
Ex.6:Hydrogen atom, say, has a radius of 0.5 Ǻ. Calculate the kinetic
energy needed by an electron to be confined to the atom.
Sol.: The radius atom is 0.5 Ǻ, therefore, the uncertainty in the
position is,
∆𝑥 = 0.5Ǻ = 0.5 × 10−10 m
h
According to the uncertainty principle, ∆𝑥∆𝑝𝑥 ≥ ℏ or ∆px ≥ ,
2π∆x

The kinetic energy needed by an electron to be confined to the atom

is,
Wave function and its physical significance:
"The quantity whose variations make a De-Broglie
wave is called wave function 𝜓 (Psi)".
"The probability amplitude of matter waves at a given
place in space at a given instant of time is
characterized by a wave function 𝜓 (x,y,z,t)". The
wave function is either real or imaginary.
According to Max Born, " the wave function itself has
no physical significance but the square of its absolute
magnitude 𝜓 2 = 𝜓𝜓 ∗ (𝜓 ∗ is the complex conjugate
of 𝜓) gives the probability of finding the particle at a
particular space and a particular time".
𝜓 2 = 𝜓𝜓 ∗
This expression is also known as probability density.
The probability of finding a particle in a volume 𝑑𝑣,
i.e., 𝑑𝑣 = 𝑑𝑥 𝑑𝑦 𝑑𝑧 , further, since the particle is
found to be somewhere in space,

A wave function satisfying the above relation is called

the normalized wave function.
The wave function 𝜓 must fulfill the following
conditions,
➢It must be finite everywhere.
➢It must be single valued.
➢It must be continuous.
 Progressive wave equation in differential form
𝑦 = 𝑎 sin(𝜔𝑡 − 𝑘𝑥) (1)
𝑑𝑦
𝑑𝑥
= −𝑘𝑎 cos(𝜔𝑡 − 𝑘𝑥)

(2)
𝑑𝑦
= 𝜔𝑎 cos(𝜔𝑡 − 𝑘𝑥)
𝑑𝑡

(3)

(2)/(3)
 Schrödinger's time independent wave equation:
Consider a system of stationary waves associated with a moving
particle. If the position of the particle is described by (x,y,z) and
𝜓 is the periodic displacement of the wave then the motion of
the wave in the differential form is given by,

Where, u is the wave velocity of the matter waves.

The solution of the above differential equation is given by,
𝜓 𝑥, 𝑦, 𝑧, 𝑡 = 𝜓0 𝑥, 𝑦, 𝑧 𝑒 −𝑖𝝎𝑡
𝝍 = 𝝍𝟎 𝒆−𝒊𝝎𝒕 𝟐
On differentiating above equation twice w.r.t. time, we get,
On substituting the value from eq.(3) in eq.(1), we get,

Since, , is known as Laplacian

operator. Thus,
From, De-Broglie's hypothesis,

If E is the total energy, V is the potential energy, then, kinetic energy of

the particle is given as,

𝑃 2 = 2𝑚(𝐸 − 𝑉)
On Substituting the value of 𝑃 2 in above equations,
𝟐 𝒎(𝑬 − 𝑽)𝜓
𝟖𝝅 𝟐𝒎(𝑬 − 𝑽)𝜓
𝛻 2𝜓 + =𝟎 𝒐𝒓, 2
𝛻 𝜓+ =𝟎 (𝟒)
𝒉𝟐 ℏ𝟐

This is an expression of Schrödinger's time independent wave equation.

 Schrödinger's wave equation for a free particle:
For a free moving particle, the potential energy of a particle is zero.
Therefore, Schrodinger's equation for a free particle is given by,
𝟖𝝅𝟐 𝒎𝑬𝜓 𝟐𝒎𝑬𝜓
𝛻2 𝜓 + = 𝟎 𝒐𝒓, 𝛻 2𝜓 + =𝟎 (𝟓)
𝒉𝟐 ℏ𝟐
Schrödinger's time dependent wave equation:
In order to obtain time dependent wave equation, if we eliminate the
energy term from Schrodinger time independent wave equation (4).
For it, let us differentiate the eq. (2) w.r.t. time, we get,
𝝍 = 𝝍𝟎 𝒆−𝒊𝒘𝒕
On multiplying by i to numerator and denominator to L.H.S., we
have,

According to the Schrodinger's time independent wave equation,

we have,
On multiplying the above equation by to both sides, we get,

The above expression is the Schrödinger's time dependent

wave equation . This equation can be modified in terms of
Hamiltonian operator (H) as follows,

So, the above equation can be written as,

𝐸𝜓 = 𝐻𝜓
The Hamiltonian operator (H) thus coincide with the energy
operator.
A Particle in a One Dimensional Box (Infinite
Square Well Potential):
Consider the particle moving inside a box along x
direction. The particle is bouncing back and forth
between the walls of the box. The box has potential
barriers at x = 0 and at x = L. In terms of boundary
conditions, the potential function is given by,
Figure. Potential function.
The wave function 𝜓 = 0 outside the box and it exists
only within the box. According to Schrödinger's time
independent wave equation for free particle in one
dimensional box is given by,

Putting the value , we have,

The general solution of the above differential equation is

given by,
𝜓 = 𝐴 sin 𝐾𝑥 + 𝐵 cos 𝐾𝑥 (3)
Where, A,B, and K are constants.
On applying the boundary conditions, we get,
𝜓 = 0 at 𝑥 = 0 ⟹ 𝐵 = 0
𝜓 = 0 at 𝑥 = 𝐿 ⇒ 0 = 𝐴 sin(𝐾𝐿)
Since, 𝐴 ≠ 0 ⇒ sin(𝐾𝐿) = 0 𝑜𝑟 𝐾𝐿 = 𝑛𝜋
𝑛𝜋
or, 𝐾= [where n = 0,1,2,3................]
𝐿
On Substituting the value of B and K in equation (3), we get,
𝑛𝜋
𝜓𝑛 = 𝐴 sin 𝑥 (4)
𝐿
𝟖𝝅𝟐 𝒎𝑬
Since, = 𝐾2
𝒉𝟐
𝑛2 𝜋 2 ℎ 2
or, 𝐸=
𝐿2 8𝜋 2 𝑚

Where, n = 1,2,3,4,----------. For each value of n, there is an energy

level and corresponding wave function is given by equation (4). Each
value of En is called eigen value and the corresponding function 𝜓𝑛 is
called eigen function.
 Wave function:
The particle is certainly found within the box. Therefore, the normalized wave
function of the particle is given by,
𝐿
න 𝜓 2𝑑𝑥 = 1
0
𝐿 2 𝑛𝜋
‫׬‬0 𝐴 sin2 𝑥 𝑑𝑥 = 1
𝐿
𝐿
2𝑛𝜋
𝐴2 න 1 − cos 𝑥 𝑑𝑥 = 1
0 𝐿
2
𝐴 𝐿 2𝑛𝜋 𝐿
(𝑥)0 −(sin 𝑥)0 = 1
2 𝐿
𝐴2 2
×𝐿 =1 ⇒𝐴 =
2 𝐿
Therefore, the wave function associated with the particle within the box is given by,

The normalized wave function 𝜓1 , 𝜓2 , 𝜓3 etc are plotted against energy level E1 , E2 ,
E3 and so on as shown in figure .
 9ℎ2
8𝑚𝐿2

4ℎ2
8𝑚𝐿2

ℎ2
8𝑚𝐿2

Figure. Normalized wave function 𝛙𝟏 , 𝛙𝟐 , 𝛙𝟑 plotted against energy level E1 , E2 , E3 .

Trajectories of a particle in a box (also called an infinite square well) in classical mechanics (A) and quantum mechanics (B-F). In (A), the
particle moves at constant velocity, bouncing back and forth. In (B-F), wavefunction solutions to the Time-Dependent Schrodinger Equation are
shown for the same geometry and potential. The horizontal axis is position, the vertical axis is the real part (blue) or imaginary part (red) of the
wavefunction. (B,C,D) are stationary states (energy eigenstates), which come from solutions to the Time-Independent Schrodinger Equation.
(E,F) are non-stationary states, solutions to the Time-Dependent but not Time-Independent Schrodinger Equation. Both (E) and (F) are
randomly- generated superpositions of the four lowest-energy eigenstates, (B-D) plus a fourth not shown.
 A Particle in a Three Dimensional Box:
In terms of boundary conditions, the potential function for three
dimension box of sides 𝐿𝑥 , 𝐿𝑦 𝑎𝑛𝑑 𝐿𝑧 is given by,

The Eigen function and Eigen energy are given by,

 Basic Postulates of Quantum Mechanics:
The three basic postulates of quantum mechanics are as,
1) Each dynamical variable relating to the motion of a
particle can be represented by a linear operator.
2) A linear eigenvalue equation can be always linked with
each operator.
3) In general, when a measurement of dynamical quantity “a”
is made on a particle for which the wave function is 𝜓, we
get the different value of “a” during different trials. This is
due to uncertainty principle. The most probable value of a
is given by,

Where, 𝐴෡ is the operator associated with the quantity “a” and

𝜓 ∗ is the complex conjugate of 𝜓. The quantity 𝑎 is called
expectation value of 𝐴෡ .
 Harmonic Oscillator:
Harmonic motion occurs when a system vibrates about an equilibrium configuration. A
body suspended by a spring or floating in a liquid, a diatomic molecule, an atom in a
crystal lattice all executes harmonic motion.
Let us consider a particle executing simple harmonic motion, then, the restoring force
‘F’ on the particle of mass m is proportional to the displacement of the particle 𝑥 from
its equilibrium position and in the opposite direction. Thus,
𝐹 = −𝑘𝑥 (1)
The potential energy of the particle is given by,
𝑥 𝑥 1
𝑉 𝑥 = − ‫׬‬0 𝐹 𝑥 𝑑𝑥 = 𝑘 ‫׬‬0 𝑥 𝑑𝑥 = 𝑘𝑥 2 (2)
2
Substituting this value for the potential energy in Schrodinger equation we get,
𝜕2 𝜓 8𝜋2 𝑚 1 2 𝜓=0
+ 𝐸 − 𝑘𝑥 (3)
𝜕𝑥 2 ℎ2 2
Let us assume the solution of above equation is,
2
𝜓 𝑥 = 𝐴𝑒 −𝑏𝑥
Differentiating it w.r.t. 𝑥, we get,
𝜕𝜓 2
= −2𝐴𝑏𝑥𝑒 −𝑏𝑥
𝜕𝑥
Differentiating it again w.r.t. 𝑥, we get,

Substituting these values in eq. (3), we get,

2
Removing the common factor 𝐴𝑒 −𝑏𝑥 , we have,

8𝜋2 𝑚𝐸 2 4𝜋2 𝑚𝑘2

− 2𝑏 + 4𝑏 − 𝑥 =0 (4)
ℎ2 ℎ2
The two sets of quantity within the brackets in eq. (4) must be separately
zero because we have to get a solution which should be valid for all values of
𝑥.
8𝜋2 𝑚𝐸 𝑏ℎ 2
− 2𝑏 = 0 ⇒ 𝐸 = (5)
ℎ2 4𝜋2 𝑚
Substituting the value of b in eq. (5), we get

The classical frequency 𝜐 is given as,

1
𝐸 = ℎ𝜐
2
This is the ground energy level for harmonic oscillator.
The general solution of equation (3) is of the form,
−𝑏𝑥2
𝜓 𝑥 = 𝐴𝑓𝑛 (𝑥)𝑒
Where, 𝑓𝑛 (𝑥) is a polynomial in which the highest power of 𝑥 is 𝑥 𝑛 .
The solution leads to the energy values,
Probable density of ground state and first three excited state.
 Applications of quantum mechanics:
Important applications of quantum mechanics are in,
1) Quantum chemistry
2) Quantum optics
3) Quantum computing
4) Superconducting magnets
5) Light emitting diodes
6) Optical amplifiers
7) Lasers
8) Transistors
9) Semiconductors
10) Microprocessor
11) Medical and research imaging
12) Electron microscopy
 Ex.7: A particle of rest mass 𝑚0 has a kinetic energy K, show that its
de-Broglie wavelength is given by,

Hence, calculate the wavelength of an electron of kinetic energy 1

MeV. What will be the value of 𝜆 if 𝐾 << 𝑚0𝑐 2? or,
A particle of rest mass 𝑚0 has a kinetic energy K. What will be the
value of 𝜆 if 𝐾 << 𝑚0 𝑐 2?

Sol.: According to the de-Broglie's concept of matter wave,

𝑚0
𝑚= ⟹ 𝑚 2𝑣 2 = 𝑐 2(𝑚 2 − 𝑚02)
𝑣2
1− 2
𝑐
Substituting this value of mv in equation (1), we get,

which is a required relation.

For an electron,

For K= 1MeV, then equation (2) becomes,

If 𝐾 << 𝑚0 𝑐 2, then, 𝐾 + 2𝑚0 𝑐 2 = 2𝑚0 𝑐 2,

Thus, the relativistic de-Broglie wavelength is reduced to non-

relativistic de-Broglie wavelength at 𝐾 << 𝑚0𝑐 2 .
Ex.8: Calculate the wavelength associated with a (i) 1
MeV electron (ii) 1MeV proton and (iii) 1MeV photon.
Sol.: (i) The rest mass of an electron is,

= 0.51 𝑀𝑒𝑉
Since, the given kinetic energy (1MeV) of an electron is
greater than its rest energy (0.51 MeV),
therefore, the relativistic de-Broglie formula is
applicable, which is given as,

= 8.75 × 10−13 𝑚
𝜆 = 8.75 × 10−3 Å
(ii) The rest mass of proton is,

= 937 × 106 𝑒𝑉 = 937 𝑀𝑒𝑉

Since, the given kinetic energy (1MeV) of proton is
less than its rest energy (937MeV),
therefore, the non-relativistic de-Broglie formula is
applicable, which is given as,

𝜆 = 2.87 × 10−4 Å
(iii) The rest mass of the photon and hence the rest mass
energy is zero. Thus, the energy of a photon is entirely
kinetic and is given by,

Here, E = 1MeV,

𝜆 = 1.24 × 10−2 Å