Introduction to

Quantum Mechanics

Probal Roy
Lecturer
Department of Physics
Bangladesh University of Engineering and Technology
Dual Nature of Matter
The dual nature mainly because the behavior of macroscopic objects is practically
particle in nature, they do have wave nature, but it is negligible because of their huge
masses; whereas on the other hand the atomic level particles have very little mass
and hence both particle and wave nature is prevalent in them. This dual behavior of
displaying both particle and wave nature is known as dual behavior of matter and
for every particle, the particle nature comes from its mass and the wave nature comes
from its matter-wave.

Classical Physics hasn’t been able to explain the dual behavior of a matter and
Heisenberg’s uncertainty principle, according to which the position and momentum
of a sub-atomic particle can be calculated simultaneously with some degree of
inaccuracy. Hence, there was a need for a new theory that could explain the behavior
of atomic and sub-atomic particles.

So, this led to the birth of quantum physics – It is a branch of science that explains
the physical phenomenon by microscopic and atomic approach and takes into
account the dual behavior of matter. It is theoretical physics, and it specifies the
laws of motion that the microscopic objects obey. When quantum mechanics is
applied to macroscopic objects (for which wave-like properties are
insignificant) the results are the same as those from classical mechanics.
De-Broglie Concept of Matter Wave:
From phenomena of Diffraction, Interference, and Polarization, It is noted that light
is one kind of wave motion. Further, some new phenomena such as Photo-electric
Effect and Compton Effect are not explained based on wave theory. But these are
explained based on quantum theory.

In quantum theory, the light or photons are assets with literature on mass, velocity,
and momentum.

But photon theory was applied to the phenomena of interference and diffraction. It
is not able to explain.

So light has dual nature, it possesses both particle and wave properties.

• In some cases, the waves are predominant and in some other cases, the
particles are predominant.

• The dual properties are depending upon the condition under which
the particular phenomena occur.

• It is noted that waves and particles are never expected to appear

together.

De-Broglie extended the wave-particle parallelism of optics to all fundamental

things existing independently from other things. Fundamental existing things like,

❖ Electron

❖ Protons

❖ Neutrons

❖ Atoms and Molecules

He suggested that matter has also dual nature i.e. wave and particle-like radiation.
There is a detailed connection between waves and written work in the case of
particles also.

A moving particle is always associated with the wave and it is controlled by wave
same as the photon is controlled by a wave.

On the concept of wave-particle duality, he noted that if the radiation (light) can act
as a wave sometimes and act as a particle at other times.

Then the material (matter) particle (electron and neutron) should act as a wave at
some other time.
So, the wavelength λ associated with any moving particle of momentum is p ( mass
m and velocity v) is given by,

𝒉 𝒉
𝝀= = … … … … … (1)
𝒑 𝒎𝒗

Where h is the Plank’s constant. Such waves associated with the matter particles
are called matter waves or de Broglie waves.

De-Broglie Wavelength:

The expression of the De-Broglie wave associated with a material particle can be
derived from a comparison of radiation. Suppose, according to Plank theory of
radiation the energy of the photon (quantum) is given, 𝐸 = ℎ𝜈
𝑐
But, 𝜈 = , c is the velocity of light, 𝜆= wavelength of light
𝜆

𝑐
𝐸=ℎ ………………… (1)
𝜆

But according to energy and mass relation,

𝐸 = 𝑚𝑐 2 …………………..(2)
Equating (1) and (2)
𝑐
𝑚𝑐 2 = ℎ
𝜆
ℎ
Hence, 𝜆= .……………………. (3)
𝑚𝑐

We know that c is the velocity of light (photon) so

𝑚𝑐 = 𝑃 ………….. (4)

[Associated with a photon (radiation)]

Now suppose a material particle of mass m and is moving with velocity 𝑣,

Hence, the momentum of a particle, 𝑃 = 𝑚𝑣

The wavelength (𝜆) is associated with particle (material particle),

𝒉 𝒉
𝝀= =
𝒎𝒄 𝑷

De-Broglie Wavelength in terms of Kinetic Energy:

Let the kinetic energy of moving material particle is
1
𝐸𝑘 = 𝑚𝑣 2
2
1 𝑚
𝐸𝑘 = 𝑚𝑣 2 ×
2 𝑚
(𝑚𝑣)2
𝐸𝑘 =
2𝑚
According to the definition of Kinetic Energy,
𝑃2
𝐸𝑘 = , where, 𝑃 = 𝑚𝑣
2𝑚

So,
 𝑃 = √2𝑚𝐸𝑘
Then, De-Broglie wavelength in the form of Kinetic Energy will be,
𝒉
𝝀=
√𝟐𝒎𝑬𝒌

De-Broglie Wavelength Associated with Electron:

Suppose, Electron is at rest. It has a mass mo and the charge of the electron is e. Now
electron is associated with potential voltage and obtained the velocity ν from its rest
position.

1
𝐸𝑘 = 𝑚𝑜 𝑣 2 = 𝑒𝑉𝑜
2

𝑚𝑜 𝑣 2 = 2𝑒𝑉𝑜

𝑚𝑜2 𝑣 2 = 2𝑚𝑜 𝑒𝑉𝑜

𝑚𝑜 𝑣 = √2𝑚𝑜 𝑒𝑉𝑜

De-Broglie wavelength is associated with electron

ℎ ℎ
𝜆= =
𝑃 𝑚𝑜 𝑣

𝒉
𝝀=
√𝟐𝒎𝒐 𝒆𝑽𝒐

For any charged particle, e=q, So,

𝒉
𝝀=
√(𝟐𝒎𝒒𝒗)
Properties of matter-wave:
𝒉 𝒉
➢ Lighter in the particle, greater is the wavelength associated with it. 𝝀 = = .
𝒎𝒗 𝑷

➢ Smaller is the velocity of the particle, greater is the wavelength associated with
it.

➢ Suppose, 𝒗 = 𝟎, then 𝝀 = ∞; wave becomes indeterminate

➢ Suppose 𝒗 = ∞, then 𝝀 = 𝟎; wave becomes a zero. These conditions suggest

that matter waves are generated by the motion of particles.

➢ These waves (𝜆 = ∞ and 𝜆 = 0) are produced whether the particles are charged
particles or the particles are un-changed.

➢ These waves are not electromagnetic waves, but they are a new kind of waves
(electromagnetic waves are produced only by the motion of charged particles).
The velocity of the material particle is not a constant while the velocity of the
electromagnetic wave is constant.

➢ The velocity of matter waves is greater than the velocity of light. This can be
𝑐2
provided as under the wave velocity 𝑉𝑝 = . As a particle velocity ν can’t exceed
𝑣

c hence 𝑉𝑝 is greater than the velocity of light.

➢ The wave and particle aspects of moving bodies can never appear together in the
same experiment. What we can say is that waves have particle-like properties and
particles have wave-like properties and the concepts are inseparably linked.
Matter-wave representation is only a symbolic representation.

➢ The wave nature of matter introduced uncertainty in the location of the position
of the particle because a wave can’t be said exactly at this point or exactly at that
 point. However, where the wave is large (strong) there is a good chance of finding
the particle while, where the wave is small there is a very small (weak) chance of
finding the particle.

Wave Packet:

➢ If several waves of different wavelengths

(frequencies) and phases are superposed
together, one would get a resultant which is Constructing a wave packet
by adding up several waves
a localized wave packet.

➢ A wave packet is a group of waves with

slightly different wavelengths interfering
with one another in a way that the amplitude
of the group (envelope) is non-zero only in
the neighborhood of the particle.

What is the Velocity of the Wave Packet?

Phase Velocity or Wave Velocity:
➢ When a monochromatic wave travels through a medium, its velocity of
advancement in the medium is called the wave velocity or phase velocity. Or,

➢ The rate at which the phase of the wave propagates in space. Or,
➢ The wave packet formed by the superposition of several waves and traveling with
the velocity of the particle behaves very much like a corpuscle. Each component
wave propagates with a definite velocity, called the wave velocity or phase
velocity (𝑉𝑝 ).

𝝎
𝑽𝒑 =
𝒌
2𝜋
Where 𝜔 = 2𝜋𝜈 is he angular frequency and k = is the wavenumber.
𝜆

Group Velocity:
➢ In practice, we came across pulses rather than monochromatic waves. A pulse
consists of several waves differing slightly from one another in frequency.

➢ A disturbance or wave packet consists of several component waves, each

traveling with slightly different velocity, the resultant velocity with which the
periodicity advances is called the group velocity (𝑉𝑔 ).

➢ So, the group velocity is the velocity with which the energy in the group is
transmitted (𝑉𝑔 ).

➢ The velocity with which the overall shape of the wave propagates through space.

➢ The individual waves travel "inside" the group with their phase velocities.
𝒅𝝎
Where, 𝑽𝒈 =
𝒅𝒌

Phase Velocity of De-Broglie's Waves:

According to de-Broglie’s hypothesis of matter waves,

𝒉
𝝀=
𝒎𝒗

The wavenumber,
 2𝜋 2𝜋𝑚𝑣
k= = ………………(i)
𝜆 ℎ

If a particle has energy 𝐸, then the corresponding wave will have frequency,

𝐸
𝜈=
ℎ
Then angular frequency will be,

𝐸
𝜔 = 2𝜋𝜈 = 2𝜋
ℎ
𝑚𝑐 2
𝜔 = 2𝜋 [Since E = 𝑚𝑐 2 ] ……(ii)
ℎ

Dividing (ii) by (i),

𝑚𝑐 2
𝜔 2𝜋 ℎ
=
𝑘 2𝜋𝑚𝑣
ℎ
𝑐2
Or, 𝑉𝑝 =
𝑣

But v is always < c (velocity of light)

So, Velocity of de-Broglie's waves, 𝑉𝑝 > c (not acceptable)

De-Broglie's waves (𝑉𝑝 ) will move faster than the particle velocity (v) and hence the
waves would leave the particle behind.

Group Velocity of De-Broglie's Waves:

A wave group having wavelength 𝜆 is composed of several component waves with

slightly different wavelengths in the neighborhood of 𝜆.
The group velocity is given by,

𝑑𝜔 𝑑𝜔/𝑑𝑣
𝑉𝑔 = = ………..(i)
𝑑𝑘 𝑑𝑘/𝑑𝑣

Suppose the de- Broglie waves associated with a particle of rest mass 𝑚𝑜 moving
with the velocity 𝑣 has the angular frequency,

𝜔 = 2𝜋𝜈
𝐸
𝜔 = 2𝜋 [Since, 𝐸 = ℎ𝜈]
ℎ

𝑚𝑐 2
𝜔 = 2𝜋 [Since, 𝐸 = 𝑚𝑐 2 ]
ℎ

𝑐2 𝑚𝑜 𝑚𝑜
𝜔 = 2𝜋 × 2
[Since, m = 2
]
ℎ
√1−𝑣2 √1−𝑣2
𝑐 𝑐

2𝜋𝑚𝑜 𝑐 2
𝜔= [Angular frequency of de-Broglie waves]
𝑣2
ℎ√1− 2
𝑐

Differentiating w.r.t velocity (v),

𝑑𝜔 2𝜋𝑚𝑜 𝑐 2 𝑑 𝑣 2 −1/2
= × (1 − 2 )
𝑑𝑣 ℎ 𝑑𝑣 𝑐
3
2 2 −2
𝑑𝜔 2𝜋𝑚𝑜 𝑐 𝑣
= × (−1/2) × (1 − 2 ) × (−2𝑣/𝑐 2 )
𝑑𝑣 ℎ 𝑐

𝑑𝜔 2𝜋𝑚𝑜 𝑣
= 3 ………………(ii)
𝑑𝑣
𝑣2 2
ℎ(1− 2 )
𝑐

𝑑𝑘 2𝜋𝑚𝑜 𝑐 2 − 𝑣 2 + 𝑣 2
= 3
𝑑𝑣 ℎ 2
2 (1 − 𝑣 )
2
𝑐
[ 𝑐2 ]
 𝑑𝑘 2𝜋𝑚𝑜
= 3 ………..(iii)
𝑑𝑣
𝑣2 2
ℎ(1− 2 )
𝑐

Dividing Eqn. (ii) by Eqn. (iii)

3
2 2
𝑣
𝑑𝜔/𝑑𝑣 2𝜋𝑚𝑜 𝑣 ℎ (1 − )
𝑐2
= 3 × =𝑣
𝑑𝑘/𝑑𝑣 2𝜋𝑚𝑜
𝑣2 2
ℎ (1 − )
𝑐2

𝑽𝒈 = 𝒗

De-Broglie wave group associated with a moving particle also moves with the
velocity of the particle.

Relation between Phase and Group Velocity:

We have the relations,

Phase velocity,
𝜔
𝑉𝑝 = …………..(1)
𝑘

Group velocity,
𝑑𝜔
𝑉𝑔 = …………..(2)
𝑑𝑘

Again, the wavenumber is given by,

2𝜋
k=
𝜆

Differentiating w.r.t 𝜆 we get,

 𝑑𝑘 2𝜋
∴ =− ……………..(3)
𝑑𝜆 𝜆2

Also, The angular frequency is, 𝜔 = 2𝜋𝜈

𝑉𝑝
Or, 𝜔 = 2𝜋 [Since, 𝑉𝑝 = 𝜈𝜆]
𝜆

Differentiating above eqn. w.r.t 𝜆 we get,

𝑑𝜔 −1 2𝜋 𝑑𝑉𝑝
= 2𝜋𝑉𝑝 2 + ( )
𝑑𝜆 𝜆 𝜆 𝑑𝜆
𝑑𝜔 −2𝜋 𝑑𝑉𝑝
= [𝑉𝑝 − 𝜆 ] …………...(4)
𝑑𝜆 𝜆2 𝑑𝜆

Dividing Eqn. 4 by 3 we get,

−2𝜋 𝑑𝑉𝑝
𝑑𝜔/𝑑𝜆 2 [𝑉𝑝 − 𝜆 ] 𝑑𝑉𝑝
= 𝜆 𝑑𝜆 = [𝑉𝑝 − 𝜆 ]
𝑑𝑘/𝑑𝜆 2𝜋 𝑑𝜆
− 2
𝜆

𝒅𝑽𝒑
𝑽𝒈 = [𝑽𝒑 − 𝝀 ]
𝒅𝝀

Which is the relation between Phase and Group Velocity.

Special case,

(i) For dispersive medium,

𝑉𝑝 = 𝑓(𝜆) i.e., 𝑉𝑝 is a function of frequency.

𝑑𝑉𝑝
Then, is usually positive quantity
𝑑𝜆

𝑑𝑉𝑝
∴ 𝑽𝒑 > 𝑽𝒈 [Since, 𝑉𝑔 = [𝑉𝑝 − 𝜆 ]]
𝑑𝜆

(ii) For non-dispersive medium (such as empty space)

 𝑉𝑝 ≠ 𝑓(𝜆) i.e., 𝑉𝑝 is not a function of frequency.

𝑑𝑉𝑝
Then, =0
𝑑𝜆

∴ 𝑽𝒈 = 𝑽𝒑

Wave Mechanical Atom Model

The most recent development in the theory of atomic structure shows that the Bohr
picture of the atoms with sharply defined electron orbit is not correct. According to
the wave mechanics developed by Heisenberg, Schrodinger and Dirac, the electrons
move around the nucleus as wave packet.

This atom model has electrons in various orbits and the electrons behave as matter
waves of wavelength λ = h/mv. The electron exists as a standing wave in each orbit.
The energy levels and the ‘orbits’ of Bohr levels are retained. Even the quantum
conditions for Bohr follow from wave mechanics. For examle, consider the electron
in the hydrogen atom as a standing wave extending in a circle round the nucleus. In
order that this wave may just occupy the circumference of a circle, the circle must
contain an intigral number of wavelengths, that is,

2𝜋𝑟 = 𝑛𝜆

Where, r is the radius of the circle and n is an integer.

But,

ℎ
𝜆=
𝑚𝑣
ℎ
So, 2𝜋𝑟 = 𝑛
𝑚𝑣

𝒉
𝒎𝒗𝒓 = 𝒏
𝟐𝝅

But mvr is the angular momentum of the electron, regarded as a particle. Hence the
angular momentum is equal to an integral multiple of h/2π.

Heisenberg’s Uncertainty Principle

Statement: The position and momentum of a particle cannot be determined
simultaneously to any desired degree of accuracy.

Taking ∆𝑥 as the error in determining its position and ∆𝑝 is the error in determining
its momentum at the same instant, the quantities are related as follows:

ℎ
∆𝑥∆𝑝 ≈
2𝜋
The product of the two errors is approximately of the order of Plank’s Constant. If
∆𝑥 is small, ∆𝑝 will large and vice versa. It means that, if one quantity is measured
accurately, the other quantity becomes less accurate.

Explanation:

In order to illustrate Heisenberg’s uncertainty principle, consider an example where

the position of an electron is measured. In order to measure the position of an object,
a photon must collide with it and return to the measuring device. Since photons hold
some finite momentum, a transfer of momenta will occur when the photon collides
with the electron. This transfer of momenta will cause the momentum of the electron
to increase. Thus, any attempt at measuring the position of a particle will increase
the uncertainty in the value of its momentum.

Applying the same example to a macroscopic object (say a basketball), it can be

understood that Heisenberg’s uncertainty principle has a negligible impact on
measurements in the macroscopic world. While measuring the position of a
basketball, there will still be a transfer of momentum from the photons to the ball.
However, the mass of the photon is much smaller than the mass of the ball.
Therefore, any momentum imparted by the photon to the ball can be neglected.

Proof of Heisenberg’s Uncertainty Principle

Consider two waves having same amplitude of A that are denoted as 𝑦1 and 𝑦2
respectively. Their wave equations can be written as,

𝑦1 = 𝐴 sin(𝜔1 𝑡 − 𝑘1 𝑥) … … … … … . (1)

𝑦2 = 𝐴 sin(𝜔2 𝑡 − 𝑘2 𝑥) … … … … … . (2)

After the superimpose to each other, they will create wave packet whose expression
can be written as,
 𝑦 = 𝑦1 + 𝑦2

𝑦 = 𝐴 sin(𝜔1 𝑡 − 𝑘1 𝑥) + 𝐴 sin(𝜔2 𝑡 − 𝑘2 𝑥)

After calculating, the expression of wave packet will be,

∆𝜔𝑡 ∆𝑘𝑥
𝑦 = 2𝐴 sin(𝜔𝑡 − 𝑘𝑥) cos ( − )
2 2

Here, each packet of waves consists of two consecutive nodes and the nodes can be
∆𝜔𝑡 ∆𝑘𝑥
found if cos ( − ) = 0.
2 2

∆𝜔𝑡 ∆𝑘𝑥 𝜋 3𝜋 5𝜋
That means, for − = , , ,……. etc, the nodes can be found.
2 2 2 2 2

For a wave packet, the conditions for getting two consecutive nodes can be written
as,

∆𝜔𝑡 ∆𝑘𝑥1 𝜋
− = (2𝑛 + 1) … … … . . (3)
2 2 2
 ∆𝜔𝑡 ∆𝑘𝑥2 𝜋
− = (2𝑛 + 3) … … … . . (4)
2 2 2

By (3) – (4), we get,

∆𝑘
(𝑥 − 𝑥2 ) = 𝜋
2 1
∆𝑘
∆𝑥 = 𝜋
2

∆𝑘. ∆𝑥 = 2𝜋 … … … … … . . (5)

2𝜋 ℎ
As we know, 𝑘 = and from De Broglie wave equation, 𝜆 = , So, we can write,
𝜆 𝑝

2𝜋𝑝
𝑘=
ℎ

So,

2𝜋
∆𝑘 = ∆𝑝 … … … … … … (6)
ℎ

From (5) and (6),

2𝜋
𝛥𝑥 ⋅ 𝛥𝑝 = 2𝜋
ℎ

𝛥𝑥 ⋅ 𝛥𝑝 ≈ ℎ

So,

𝒉
𝜟𝒙 ⋅ 𝜟𝒑 ≥
𝟐𝝅

This is the equation that implies the uncertainity of position and momentum.
Uncertainty Principle for energy and time
Consider a wave packet moving with group velocity 𝑣𝑔 .So, according to the
definition of group velocity,

𝛥𝑥
𝑣𝑔 = … … … … … . (1)
𝛥𝑡

If E be the energy of the packet, then, obviously,

𝐸 = 𝑓(𝑝)

𝜕𝐸
𝛥𝐸 = 𝛥𝑝 … … … … . . (2)
𝜕𝑝

𝜕𝐸
As, = 𝑣𝑔 , then from (2),
𝜕𝑝

𝛥𝐸 = 𝑣𝑔 𝛥𝑝

Substituting the value of (1),

𝛥𝑥
𝛥𝐸 = 𝛥𝑝
𝛥𝑡

𝛥𝐸. 𝛥𝑡 = 𝛥𝑥. 𝛥𝑝

As,
ℎ
𝛥𝑥 ⋅ 𝛥𝑝 ≥
2𝜋

Then

𝒉
𝜟𝑬. 𝜟𝒕 ≥
𝟐𝝅

This is the expression of the equation that represents the uncertainty of energy and
time.
 Operator Physics

Probal Roy
Lecturer
Department of Phytysics
Bangladesh University of Engineering and Technology
Commutator:
A commutator in quantum mechanics tells us if we can measure two 'observables' at the same
time. If the commutator of two 'observables' is zero, then they can be measured at the same time,
otherwise there exists an uncertainty relation between the two.

Suppose α and β are two quantum operators. The commutator of these two operators be defined
as,

[𝛼, 𝛽] = αβ − βα

These two operators are said to be commute each other if,

[𝛼, 𝛽] = αβ − βα = 0

αβ = βα

In that case, these quantum operators can be measured at the same time.

Again, these two operators do not commute to each other if,

[𝛼, 𝛽] = αβ − βα ≠ 0

Example:
 𝜕 𝜕
Let 𝛼 = and 𝛽 = 𝑉(𝑥, 𝑡). If ψ is the wave function, then, the commutator [ , 𝑉] operates on
𝜕𝑥 𝜕𝑥

ψ by,

𝜕 𝜕 𝜕
[ , 𝑉] 𝜓 = ( 𝑉 − 𝑉 ) 𝜓
𝜕𝑥 𝜕𝑥 𝜕𝑥

𝜕 𝜕 𝜕𝜓
[ , 𝑉] 𝜓 = (𝑉𝜓) − 𝑉
𝜕𝑥 𝜕𝑥 𝜕𝑥

𝜕 𝜕𝑉 𝜕𝜓 𝜕𝜓
[ , 𝑉] 𝜓 = 𝜓+𝑉 −𝑉
𝜕𝑥 𝜕𝑥 𝜕𝑥 𝜕𝑥

𝜕 𝜕𝑉
[ , 𝑉] 𝜓 = 𝜓
𝜕𝑥 𝜕𝑥

Cancelling the commutation factor ψ, we get,

𝝏 𝝏𝑽
[ , 𝑽] =
𝝏𝒙 𝝏𝒙
Postulates of Quantum
Mechanics

Probal Roy
Lecturer
Department of Phytysics
Bangladesh University of Engineering and Technology
1st Postulate: (Operator Replacement Operator)
2nd Postulate: (Wave Function Postulate)
3rd Postulate: (Process of Measurement)
4th Postulate: (Time Dependence of ψ)

5th postulate: (Momentum Measurement)

6th Postulate: (Expectation Value)
7th Postulate: (Uncertainty Measurement)
Schrödinger’s Equation
and its applications

Probal Roy
Lecturer
Department of Phytysics
Bangladesh University of Engineering and Technology
Steady State form of Schrӧdinger equation (Time independent
Schrӧdinger equation
Properties of ψ
Applications of Schrӧdinger equation