Quantum

Mechanics

PHYSICS

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Quantum Mechanics
In this chapter, we are going to discuss basic ideas and experimental facts that lead to
the birth of a new branch of physics and helped us in understanding the microphysical
phenomena know as quantum mechanics that were observed and discovered around
the late 19th and early 20th century.

As we know initially classical mechanics were used for explaining the theory of
electromagnetism and thermodynamics. But classical physics failed to explain several
microscopic phenomena like Blackbody radiation, photoelectric effect, atomic stability,
atomic spectra, etc., lead to the foundation for Quantum mechanics.

The first breakthrough was done by Max Plank when he introduced the new concept of
quantum of energy. Which helped us in understanding the phenomenon of Blackbody
radiation.

i.e., According to Plank’s assumption, the energy exchanged between an

electromagnetic wave of frequency ν and matter can only occur as multiple of hν, which
he termed energy of a quantum.

Here,

h = Plank’s constant

ν = frequency of Electromagnetic waves

Later based on Plank’s assumption Einstein explained the photoelectric effect which
solidified Plank’s hypothesis and later these concepts are used by Niels Bohr for
explaining discrete states of energy and the interaction of atoms with radiation.

Davisson and Germer Experiment

 De-Broglie hypothesized that since nature loves symmetry, like radiation, the matter
should also have a wave nature. This was experimentally confirmed by Davisson
and Germer in 1927.

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 In the experiment, electrons are emitted from an electron gun and allowed to strike a
nickel crystal. On striking the crystal, the electrons scatter in all directions. The
intensity of the scattered beam is detected by a detector.

 Graphs are plotted between the intensity of the scattered beam and f, the angle
between the incident and scattered direction of the electron beam.

 Inferences drawn from these graphs proved the wave nature of matter.

De Broglie Hypothesis
It was De Broglie who first proposed that not only light possesses both wave and
particle properties but rather particles with mass such as electrons do as well and this
hypothesis is known as De Broglie Hypothesis.

De Broglie wavelength (λ) is the wavelength of these material waves where E is the
energy of the particle.

Thus, from the relation between linear momentum p and energy E of the particle, we
knew that , where c is the speed of light in a vacuum now by using Einstein’s
relation of energy the previous equation can be modified as

Using this equation De Broglie proposed that for a particle moving with total energy E
and momentum p has defined frequency and wavelength of oscillation just like photons

thus the wavelength of such oscillation can be expressed as , where v is

the velocity of particle and m is the mass of the particle

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Whereas the kinetic energy of a particle moving with velocity v it can be expressed as

Now for electron h, m, q is constant thus the above equation can be modified as

De-Broglie wavelength of particles in thermal

equilibrium
If a particle is in thermal equilibrium at some temperature T, then the De-Broglie
wavelength associated with it can be expressed as

Here,

T = temperature at any instance

Ek = kinetic energy of the particle at thermal equilibrium

Example:

Q: If an electron is accelerated by applying a potential difference of 400 V. What

will be the De Broglie wavelength of this electron?

A:

Given that,

V = 120 V

Now according to De Broglie’s hypothesis, the wavelength of an electron accelerated

by 400 V potential difference can be given as

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Velocity of De Broglie waves

To understand the phenomenon of group and phase velocity let's consider an example
of the simple race track in which initially it appears that all group of participants is
running with same speed but as time pass by group spread out since each participant
will be running with different speed.

In this case, the velocity of individual participants can be considered as phase velocity
vp and the average velocity of a group as a whole is considered as group velocity v g, as
shown in the figure below.

Phase Velocity:
The phase velocity of a wave is the rate at which the phase of the wave propagates in
space.

Phase velocity

Also

Case 1:

The phase velocity of atomic waves in the non-relativistic frame of reference

Here,

vp = phase velocity of De-Broglie wave in the non-relativistic frame of reference

c = speed of light

E = total energy = mc2

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p = linear momentum = mv

Note:

In this case since v ≪ c, the phase velocity of the atomic particle is always greater
than c as we can see in the above equation

Case 2:

The phase velocity of atomic waves in the relativistic frame of reference

Note:

According to the theory of relativity velocity of any wave cannot be greater than the
velocity of light c hence in a relativistic frame de-Broglie wave cannot be harmonic
waves.

Also, we must note that wave packets are only theoretical concepts used for
visualizing various phenomena in the micro-world.

Group Velocity:
The group velocity of a wave is the velocity with which the overall envelope shape of
the wave's amplitudes propagates through space.

Group velocity,

Relation between group and phase velocity:

The relation between an individual component of group and phase velocity can be
expressed as

Note:

In general group velocity is less than phase velocity (i.e., v g < vp), but for non
dispersing medium vg = vp

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Heisenberg’s Uncertainty Principle

It states that it is impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of an electron.

 Linear momentum and Displacement relation

Mathematically, it can be given as

 Energy-Time relation

Similarly, there is also the relation between uncertainty in time and energy and it states
that it is not possible to determine both the energy and the time coordinate of a particle
with unlimited precision

And it is mathematically given as

Were

∆x = the uncertainty in position

∆px (or ∆v) = the uncertainty in momentum (or velocity) of the particle.

ΔE = uncertainty in time

Δt = uncertainty in time

h = Plank’s constant

also

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Q: The position of a particle is measured with an uncertainty of 6.6 × 10-10 m.

What is the minimum uncertainly in any simultaneous measurement of the
momentum of the particle? (h = 6.63 × 10-34 J s)

A:

Given that,

Δx = 6.6 × 10-10 m

h = 6.63 × 10-34 J s

And according to the uncertainty principle

Wave function & Probability

interpretation of wave function
 As we know light waves consists of variation of electric and magnetic field
vibrating perpendicular to each other, whereas wave can be defined as some
variation in quantity with position and time.

 Similarly, a quantity used for microparticle knows as wavefunction ψ, which is

used in describing certain properties of the wave as a function of position and
time, and in one dimension it is generally expressed as ψ(x,t).

 However, it does not have any physical significance since it is not an observable
quantity and generally it is a complex-valued function.

 The wave function of a particle, at a particular time, contains all the information
that anybody at that time can have about the particle.

 But the wave function itself has no physical interpretation. It is not measurable.
However, the square of the absolute value of the wave function has a physical
interpretation.

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Probability interpretation of wave function

In 1926 Max Bohr provided a probability interpretation of the wavefunction. According

to his suggestion, the probability of finding a particle in a particular region is directly
proportional to the square of the magnitude of wave function i.e., |ψ|2.

Either probability, P of finding the particle in some infinitesimal small volume dV

(dx.dy.dx) is proportional to |ψ (x,y,z,t)|2.dV at time t

In simple terms

 For one dimension, we interpret |ψ(x,t)|2 as a probability density, a probability per

unit length of finding the particle at a time t at position x.

 The probability of finding the particle at time t in an interval ∆x about the position x
is proportional to |ψ(x,t)|2∆x.

 This interpretation is possible because the square of the magnitude of a complex

number is real and in the above equation, ψ is also known as a probability
amplitude.

Normalization of wavefunction
To understand this let’s take an example of a closed system in which there is n num-
ber of gas molecules. Now in general inside the closed system, all the gas mole-
cules will be evenly distributed as shown below.

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Now what will be the probability density of finding all the particles at some volume
ΔV, it will be extremely low but still, it’s possible similarly if we find probability density
of all such combination, we know that summation of its probability density will be
equal to 1. In simple terms, this is known as the Normalization of a wavefunction

Now since we are sure that all particle must exist somewhere in space, the equation
for normalized wave function is given as

here ΔV is volume, ψN is known as a normalized wave function, C is normalization

constant and the above condition is known as a normalizing condition.

Condition for a well-behaved wavefunction

For the probability interpretation to make sense, the wave function must satisfy
certain conditions. We should be able to find the particle somewhere, we should only
find it at one place at a particular instant, and the total probability of finding it
anywhere should be one. This leads to the requirements listed below.

The wave function (ψ) must be

1) Finite: The wavefunction ψ must be finite everywhere. i.e., it must not

tend toward infinity (x, y, z→ ∞). If the value of wavefunction is infinite it
means the probability of finding that particle at that position is
infinitesimally large, which violates the uncertainty principle. The probability
of finding the particle at time t in an interval ∆x must be some finite number
between 0 and 1.

2) Single valued: Any physical quantity can only have only 1 value at a
point. Hence the wavefunction related to that physical quantity can only
have one single value at that instance. Since having more than one value
means have multiple probabilities at that point.

3) Continuous: Wavefunction must be continuous at all boundary

conditions since it is related to a physical quantity it cannot be
discontinuous at any instance.

Thus the wavefunction which satisfies this condition is termed as well behaved
wavefunctions.

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Schrödinger’s wave equation

 Schrödinger’s wave equation is a mathematical expression describing
the energy, momentum, and position of the electron in space and time.

 The Schrödinger equation (also known as Schrödinger’s wave equation) is a partial

differential equation that describes the dynamics of quantum mechanical systems via
the wave function.

 There are two variants of Schrödinger’s wave equation based on its condition.

Time-dependent Schrödinger’s wave equation

According to the time-dependent Schrödinger wave equation for one dimension.

For three dimension the above equation can be modified as

Were,

Time independent Schrödinger’s wave equation

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This is a final form of Schrödinger’s wave equation which is independent of time-

variable and it is expressed as

Note:

By comparing both time-dependent and independent Schrödinger’s wave equation we

can see that both are similar and we can establish the relation , and this
relation of energy is known as the Energy operator in quantum mechanics.

Pauli Exclusion Principle

Pauli exclusion principle states that in a single atom no two electrons will have an
identical set or the same quantum numbers

i.e., every electron should have or be in its own unique state (singlet state).

There are two salient rules that the Pauli Exclusion Principle follows:

1) Only two electrons can occupy the same orbital.

2) The two electrons that are present in the same orbital must have opposite
spins or they should be antiparallel.

However, Pauli Exclusion Principle does not only apply to electrons.

It applies to other particles of half-integer spin such as fermions. It is not relevant

for particles with an integer spin such as bosons which have an asymmetric wave
function

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Quantum Mechanical Model of Atom

 As we discussed quantum mechanics is a theoretical science that deals with the

study of the motions of macroscopic objects that have both observable wave-like
and particle-like properties.

 A large number of orbitals are possible in an atom. Qualitatively these orbitals can
be distinguished by their size, shape, and orientation. An orbital of smaller size
means there is more chance of finding the electron near the nucleus.

 Each orbital is designated by three quantum numbers labeled as n, l, and ml.

 The principal quantum number ‘n’ is a positive integer with a value of n = 1, 2,

3....... An electron is characterized by four quantum numbers n, m, l, and s.

 Now Pauli's exclusion principle states that every electron must have its unique set
of these four quantum numbers. i.e., No two electrons can have the same set of
quantum numbers.

 There are four quantum numbers n, l, m, s which are used to identify the state of
an electron.

 Thus, Pauli’s exclusion principle defines the electronic configuration of several

subshells existing in a shell and the number of electrons entering each subshell.

 Hence, based on Pauli’s exclusion principle, the manifestation of the band

structure in solids can be explained.

Quantum number Significance Values Properties

n is the principal It signifies the energy and size of a Orbital size and
1, 2,.., n
quantum number shell and has values 1,2,3… energy level
ml is called the It signifies the orientation of a
magnetic quantum subshell and has values - l to + l -l to +l Orbital Orientation
number including zero.

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Quantum number Significance Values Properties

l is called the It signifies the shape of a shell

azimuthal quantum
And has values 0, 1, 2, 3,.., (n-1) Orbital Shape
number or orbital
quantum number i.e., l = 0, 1, 2, .......... (n - 1)

It denotes the spin state of an

s is called the spin Electron Spin
quantum number. direction
electron and has values

Example:

Q: The quantum mechanical model of the hydrogen atom requires that if the
principal quantum number is 4, the number of different permitted
orbital quantum numbers will be:

A:

Given

n=4

Thus, if the principal quantum number is 4 (i.e., n = 4),

the number of different permitted orbital quantum numbers will be (l = 0 to n – 1)

Thus, total values of l can be

l =0, 1, 2, 3.

Either there 4 different permitted orbital quantum numbers as shown above when n = 4

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The above figure represents how the shape of orbital changes for different orbital or azimuthal
quantum number

The above figure represents how the energy level of an electron can change with change in
principle quantum number across K, L, M, and N shells.

The above figure represents how orientation changes with change in magnetic quantum number

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Distribution function according to

quantum statistics
 The distribution or probability density functions describe the probability that parti-
cles occupy the available energy levels in a given system.

 The derivation of such probability density functions can be found in one of the many
statistical thermodynamic references as well as it has far-reaching application in
solid-state physics.

Fermi Dirac Distribution

 The Fermi-Dirac distribution function, also called the Fermi function, provides the
probability of occupancy of energy levels by Fermions.

 Fermions are half-integer spin particles, which obey the Pauli exclusion principle.

 The Pauli exclusion principle postulates that only one Fermion can occupy a single
quantum state.

 Therefore, as Fermions are added to an energy band, they will fill the available
states in an energy band just like water fills a bucket.

 The mathematical form of Fermi Dirac Distribution is

Bose-Einstein Distribution

 The Bose-Einstein distribution function applies to bosons. Bosons are particles with
integer spin and include photons, phonons, and a large number of atoms.

 Bosons do not obey the Pauli exclusion principle so that any number can occupy a
single energy level.

 The mathematical form of the Bose-Einstein Distribution function is

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Maxwell Boltzmann

 The Maxwell Boltzmann applies to non-interacting particles, which can be

distinguished from each other.

 This distribution function is also called the classical distribution function since it
provides the probability of occupancy for non-interacting particles at low densities.

 Atoms in an ideal gas form a typical example of such particles.

 The Maxwell-Boltzmann distribution function is given by

Here,

E = Energy value at a certain level

Ef = Fermi energy

k = Boltzmann constant

f(E) = Fermi factor, Fermi function or occupancy probability

Example:

Q: The occupancy probably P(E) according to Fermi-Dirac statics

is

a quantum state whose energy is 0.01 eV above the Fermi energy is about
______. Assume a sample temperature of 800 K

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A:

Given E – EF = 0.01 eV

T = 800

k =1.380649 × 10−23 J/K = 8.617 333 262... x 10-5 eV/ K ≈

kT = T/11600 = 800/11600 = 0.069 eV

Now according to Fermi-Dirac statics we can say

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