UNIT - I: QUANTUM PHYSICS AND SOLIDS

Quantum Mechanics: Introduction to quantum physics – de-Broglie hypothesis – Davisson and

Germer experiment –Heisenberg uncertainty principle – Born interpretation of the wave function
– time independent Schrodinger wave equation – particle in one dimensional potential box.
Solids: Classical and Quantum Free electron theory – Bloch’s theorem – Kronig-Penney model,
Origin of energy bands – classification of solids.

Introduction
Advances in solid state physics are made by using the principles of Quantum mechanics.
The energy of the electron in the solid, black body radiation, Spectra of solids, magnetism,
superconductivity, etc., are all explained only by quantum mechanics.
At the end of the 19th century, physicists had every reason to regard the Newtonian laws
governing the motion of material, and laws of electromagnetism, as fundamental laws of Physics.
They believed that there should be some limitation on the validity of these laws which constitute
“classical mechanics” to understand the submicroscopic world of the atom and its constitutes,
which became necessary to introduce new ideas and concepts, which in turn led to the
mathematical formulation of “Quantum mechanics” during 1900s. This had no immediate and
spectacular success in the explanation of the experimental observations. Quantum mechanics
provided the key to the understanding of the behavior of very small objects like the atoms and it
constitutes. The failure of classical mechanics was very evident to explain the existence of atom,
blackbody radiation, Photoelectric effect and Compton effect. This led to the understanding of a
new adaptation of physics to understand the behavior of subatomic particles, which was named as
Quantum Physics.
In this unit, we will study the development of the Quantum mechanics, de Broglie
hypothesis, Heisenberg’s uncertainly principle, Schrödinger’s wave equation and its application.

deBroglie’s hypothesis:
As electromagnetic waves behave like particles and Particles like electrons will behave like
waves called matter waves. The matter waves thus conceived by de-Broglie are de-Broglie matter
waves. He derived an expression for the wavelength of matter waves on the analogy of radiation
Based on the Planck’s theory of radiation, the energy of a photon (Quanta) is given by,

𝐸 = ℎ𝛾

Since, 𝛾 = 𝑐/𝜆,
ℎ𝑐
𝐸= ……………………………… (1)
𝜆
Where, c is the velocity of light, and λ is the wavelength of light.

According to Einstein’s mass energy relation,

𝐸 = 𝑚𝑐 2 ………………………….. (2)
ℎ𝑐
From equations (1) and (2) 𝑚𝑐 2 = 𝜆

hc h h
λ = mc2 = mc = p………………………………….(3),
where P = momentum of photon and λ is the De-Broglie wavelength associated with a photon.
de-Broglie proposed the concept of matter waves, according to which a material particle of
mass ‘m’ moving with velocity ‘ ’ should be associated with de-Broglie wavelength ‘λ’ given by
ℎ ℎ
𝜆 = 𝑚𝑣 = 𝑝 ………………………………………(4)

This is called de-Broglie’s wave equation.

Where: 𝑝 = 𝑚𝑣, momentum associated with particle.

De-Broglie suggested that this equation for wavelength is a perfectly general one, applying
to, material particles as well as to photons.
If E is the kinetic energy of particle, then the De-Broglie’s wave length is given by,
1
E= mv2
2

𝑚2 𝑣 2
𝐸= 2𝑚
𝑝 = √2𝑚𝐸
h h
λ = mV = p

hence de=Broglie wave length

h
λ= ……………………………….(5)
√2m𝐄

De-Broglie’s wave length of Electron:

If m0 is the rest mass of electron and it is accelerated with a potential V. if v

is the velocity attained by electron due to acceleration.
The kinetic energy of electron
1
𝐸 = 2 𝑚0 𝑣 2 …………………………….(1)

Energy of electron due to application of potential,

𝐸 = 𝑒𝑉…………………………………(2)
 From 1 and 2,
1
𝑒𝑉 = 𝑚𝑣 2
2
2eV = m𝑣 2
Multiply by ‘m’ on both sides we get
2meV=𝑚2𝑣2
mv =√2𝑚𝑒𝑉

From de-Broglie general equation

h h
λ= =
mv p
h
λ=
√2meV

Where h is planks constant, h=6.625 ×10−34J-S, mo is rest mass of the electron

𝑚o=9.1×10−31k𝑔 and e is the charge of electron e=1.6×10−19𝑐.
Substitute above values in eq (7), we get
12.27
λ= Å
√V
The above expression is for non-relativistic case, since relative variation of mass with
velocity is not considered. Thus the accelerated electrons exhibit wave nature corresponding to
wave length of x rays. This concept helped Davisson & Germer to provide experimental evidence
on matter waves when they conducted electron diffraction experiments.

Characteristics of Matter waves:

h
Since λ = mv

1. Lighter the particle, greater is the wavelength associated with it.

2. Lesser the velocity of the particle, longer the wavelength associated with it.
3. For v = 0, λ = ∞. This means that only with moving particle, matter waves is associated.
4. Whether the particle is changed or not, matter waves is associated with it.
5. It can be proved that matter waves travel faster than light. We know that E = h ν and
E = m c2
hν = mc2 or ν = m c2/ h
Wave velocity (ω) is given by
 ω = ν λ = m c2 λ/ h = (m c2 / h) (h / m v)
 ω =c2/v
As the particle velocity ‘v’ cannot exceed velocity of light, ω is greater than the velocity of light.
6. No single phenomena exhibit both particle nature and wave nature simultaneously.
7. The wave nature of matter introduces an uncertainty in the location of the particle &
the momentum of the particle exists when both are determined simultaneously.

Davisson and Germer’s experiment

C. J. Davisson and L. H. Germer were studying scattering of electrons by a metal target and
measuring the intensity of electrons scattered in different directions.
Experimental Arrangement:
An electron gun, which comprises of a tungsten filament is heated by a low tension battery
B1, produces electrons. These electrons are accelerated to desired velocity by applying suitable
potential from a high tension source B2. The accelerated electrons are collimated into a fine beam
by allowing them to pass through a system of pin holes provided in the cylinder. The whole
instrument is kept in an evacuated chamber.
The past moving beam of electrons is made to strike the Nickel target capable of rotating
about an axis perpendicular to the plane. The electrons are now scattered in all directions by the
atomic planes of crystals. The intensity of the electron beam scattered in a direction can be
measured by the electron collector which can be rotated about the same axis as the target. The
collector is connected to a galvanometer whose deflection is proportional to the intensity of the
electron beam entering the collector.
The electron beam is accelerated by 54 V is made to strike the Nickel crystal and a sharp maximum
is occurred at angle of 50o with the incident beam. The incident beam and the diffracted beam in
this experiment make an angle of 65o with the family of Bragg’s planes.
d = 0.091nm (for Ni crystals)
According to Bragg’s law for maxima in diffracted pattern,
2d sin θ = n λ

For n =1, λ = 2d sin θ

2d sin θ = 2 x0.91x 10-10x sin 65o

= 0.165 nm
 Fig. Davisson and Germer's Apparatus [5]

Figure: (a) The variation of the intensity of scattered electrons with

the direction of scattering and (b) nickel crystal acting as a grating

For a 54 V electron, the DeBroglie wavelength associated with the electron is given by
12.27
λ= Å
√V
12.27
λ= Å
√54
= 0.166 nm.
This value is in agreement with the experimental value. This experiment provides a direct
verification of De Broglie hypothesis of wave nature of moving particles.
Heisenberg Uncertainity Principle:
According to classical mechanics, a moving particle at any instant has a fixed position in
space and a definite momentum which can be determined simultaneously with any desired
accuracy. The classical point of view represents an approximation which is adequate for the objects
of appreciable size, but not for the particles of atomic dimensions.
Since a moving particle has to be regarded as a de Broglie group, there is a limit to the accuracy
with which we can measure the particle properties. The particle may be found anywhere within
the wave group, moving with the group velocity. If the group is narrow, it is easy to locate its
position but the uncertainty in calculating its velocity or momentum increases. On the other hand,
if the group is wide, its momentum can be estimated satisfactorily, but the uncertainty in finding
the location of the particle is great. Heisenberg stated that the simultaneous determination of exact
position and momentum of a moving particle is impossible.
If Δx is Error in the measurement of position of the particle along X-axis Δp is Error in
the measurement of momentum

Then ΔX. ΔP ≥ h/4π ……………………………………………………..(1)

Where h is Plank’s constant

The above relation represents the uncertainty involved in measurement of both the position
and momentum of the particle.
To optimize the above error, lower limit is applied to the eqn. (1)

Then (Δ x). (Δ p) ≥ /2

Where =h/2Π
A particle can be exactly located (Δ x → 0) only at the expense of an infinite momentum
(Δp → ∞).

There are uncertainty relations between position and momentum, energy and time, and
angular momentum and angle.
If the time during which a system occupies a certain state is not greater than Δ t, then the
energy of the state cannot be known within Δ E,
i.e., (Δ E) (Δ t) ≥ ђ / 2
Schrodinger’s Time Independent Wave Equation
Schrödinger, in 1926, developed wave equation for the moving particles. One of its forms
can be derived by simply incorporating the de-Broglie wavelength expression into the classical
wave eqn.
If a particle of mass moving with velocity ‘v’ is associated with a group of waves.

Let  be the wave function of the particle. Also let us consider a simple form of progressing
wave like the one represented by the following equation,
 = 0 sin (t – k x) ------------------ (1)

Where = (x, t) and 0 is the amplitude

Differentiating  partially w.r.to x,

𝛛𝚿
=0cos (t – kx) (– k) = – k 0cos (t – kx)
𝝏𝒙

Once again differentiate w.r.to x,

𝛛𝟐 𝚿
= (– k) 0(– sin (t – k x)) (– k)
𝝏𝒙𝟐

𝛛𝟐 𝚿
= – k20 sin (t–kx)
𝝏𝒙𝟐

𝛛𝟐 𝚿
= – k2 (from Eq (1))
𝝏𝒙𝟐

𝛛𝟐 𝚿
+ k2= 0 -------------------------------------------------(2)
𝝏𝒙𝟐

𝛛𝟐 𝚿 𝟒𝝅𝟐 𝟐𝝅
+ ( 𝝀𝟐 )= 0 ---------------------------------------------(3) (since k = )
𝝏𝒙𝟐 𝝀

From eqn. (2) or eqn. (3) is the differential form of the classical wave eqn.

now we incorporate de-Broglie wavelength expression = h/mv.

𝛛𝟐 𝚿 𝟒𝝅𝟐
Thus, we obtain, + 𝒉 𝟐 𝜳= 0
𝝏𝒙𝟐 ( )
𝒎𝑽

∂2 Ψ 4𝜋 2 𝑚2 𝑉 2
+ 𝛹= 0-------------------------------(4)
𝜕𝑥 2 ℎ2

The total energy E of the particle is the sum of its kinetic energy K.E and potential energy V
Total Energy=kinetic Energy+ Potential Energy

i.e., E = K.E + V -----------(5)

K.E = E – V
𝟏 𝒎 𝒎𝟐 𝒗 𝟐
and K.E = 𝟐 𝐦𝒗𝟐 × 𝒎 = ---------(6)
𝟐𝒎

Therefore, m2v2 = 2 m (E – V) ------------(7)

Substitute equation (7) in (4), we get
𝛛𝟐 𝚿 𝟖𝝅𝟐 𝒎
+[ (E-V)] = 0 ------------(8)
𝝏𝒙𝟐 𝒉𝟐

In quantum mechanics, ђ=h/2𝝅

 𝛛𝟐 𝚿 𝟐𝒎
+ [ ђ𝟐 (E -V)]= 0 ------------(9)
𝝏𝒙𝟐

For simplicity, we considered only one -dimensional wave.

Extending eqn. (9) for a three -dimensional, we get
𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝟐𝒎
+ + + [ ђ𝟐 (E -V)]= 0 ------------(10)
𝝏𝒙𝟐 𝝏𝒚𝟐 𝝏𝒛𝟐
𝟐𝒎(𝑬−𝑽)
𝛁𝟐𝛙 + 𝛙=𝟎
ђ𝟐

This is known as three-dimensional Schrodinger wave equation.

∂ ∂ ∂ 𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿
(𝑤ℎ𝑒𝑟𝑒 ∇ = i ∂x + j ∂y + k ∂z and ∇2 = + + )
𝝏𝒙𝟐 𝝏𝒚𝟐 𝝏𝒛𝟐

Physical Significance of Wave Function:

Max Born in 1926 gave a satisfactory interpretation of the wave function  associated with
a moving particle. He postulated that the square of the magnitude of the wave function ||2
(or *), evaluated at a particular point represents the probability of finding the particle at the
point.
||2 is called the probability density and  is the probability amplitude. Thus the probability
of the particle within an element volume d is ||2 d. Since the particle is certainly somewhere,
the integral at ||2 d over all space must be unity i.e.,

-

||2 .d = 1
A wave function that obeys the above equations is said to be normalized. Energy
acceptable wave function must be normalizable besides being normalizable; an acceptable wave
function should fulfill the following requirements (limitations)
It must be finite everywhere. It must be single valued.
It must be continuous and have a continuous first derivative everywhere.

Normalization of a wave function:

Since |(x, y, z)| 2.d is the probability that the particle will be found in a volume element d.
Surrounding the point at position (x, y, z), the total probability that the particle will be somewhere in space
must be equal to 1. Thus, we have

-

|(x, y, z) 2|.d = 1
 Where  is a function of the space coordinates (x, y, z) from this ‘normalization condition’
we can find the value of the complaint and its sign. A wave function which satisfies the above
condition is said to be normalized (to unity).
The normalizing condition for the wave function for the motion of a particle in one
dimension is

-

|(x) |2 .dx = 1

From these equations, we see that for one – dimensional case, the dimension of 
(x) is L and for the three dimensional case the dimension of (x, y, z) is L-3/2.
-1/2

Particle in One Dimensional Potential Box

Consider a particle of mass ‘m’ placed inside a one-dimensional box of infinite height
and width L.

Fig. Particle in a potential well of infinite height. [6]

Assume that the particle is freely moving inside the box. The motion of the particle is restricted
by the walls of the box. The particle is bouncing back and forth between the walls of the box at x
= 0 and x = L. For a freely moving particle at the bottom of the potential well, the potential energy
is very low. Since the potential energy is very low, moving particle energy is assumed to be zero
between x =0 and x = L.
The potential energy of the particle outside the walls is infinite due to the infinite P.E.
The particle cannot escape from the box
i.e. V = 0 for 0 < x < L ----- (1)
V = ∞ for 0 ≥ x ≥ L ------ (2)
Since the particle cannot be present outside the box, its wave
function is zero i e │ψ│ = 0 for 0>x>L
│ψ│ = 0 for x = L & x = 0
 The Schrödinger one – dimensional time independent eqn. is

𝜕 2 𝜓 2𝑚(𝐸 − 𝑉)𝜓
+ =0
𝜕𝑥 2 ℏ2
For a free particle V = 0

𝜕 2 𝜓 2𝑚(𝐸)𝜓
+ =0
𝜕𝑥 2 ℏ2

Taking (2 m E / ℏ2 ) = K2 -------------------------
(3)

𝜕2𝜓
+ 𝑘 2 𝜓 = 0 ------ (4)
𝜕𝑥 2

Eqn. (1) is similar to eq. of harmonic motion and the solution of above eqn. is written as
Ψ = A sin kx + B cos kx ----------- (5)
where A, B and k are unknown quantities. T o calculate them it is necessary to construct
boundary conditions.
Hence boundary conditions are,
When x = 0, Ψ = 0 => from (5) 0 = 0 + B => B = 0--------- (6)
When x = L, Ψ = 0 => from (5) 0 = A sin kL + B cos kL ----------(7)

But from (6) B = 0 therefore eqn. (7) may turn as

A sin kL = 0

Since the electron is present in the box 𝑎 ≠ 0

sin 𝑘𝐿 = 𝑛𝜋
𝑛𝜋
So, 𝑘 = ----- (8)
𝐿

Calculation of Eigen Values of Energy:

𝑛𝜋 2
𝑘2 = ( )
𝑎

8π2 𝑚𝐸 𝑛2 𝜋 2
= 2
ℎ2 𝑎
𝑛2 ℎ 2
𝐸 = 8𝑚𝑎2
 𝒏𝟐 𝒉 𝟐
𝑬𝒏 = 𝟖𝒎𝒂𝟐 ....................... (9)

This equation gives the allowed values of energy for different values of n.
The lowest energy of a particle is given by putting n=1 in the equation (8)
ℎ2
𝐸1 = 8𝑚𝑎2 is the lowest energy, minimum energy, ground state energy or zero-point

energy of the system.

𝐸𝑛 = 𝑛2 𝐸1

From the above equation, it is clear that

1) The lowest energy of the particle is obtained by putting n = 1
ℎ2
𝐸1 =
8𝑚𝐿2
This is known as zero point energy of the system. Notice that the lowest possible energy is
not zero. Notice that as the quantum number increases, the wavefunction becomes more
oscillatory. For n = 2, the wavefunction is zero at the midpoint of the box x = L/2. This point is a
node of this wavefunction. A node refers to a point (other than boundary points) where the
wavefunction goes to zero. For the particle in a 1D box, we see that the number of nodes is equal
to n − 1.

And also 𝐸𝑛 = 𝑛2 𝐸1
Normalization of the wavefunction:
𝑛𝜋𝑥
𝜓𝑛 = 𝐴𝑠𝑖𝑛 , 𝑓𝑜𝑟 0 < 𝑥 < 𝑎…………………………………..(10)
𝑎

𝜓𝑛 = 0, 𝑓𝑜𝑟 0 ≥ 𝑥 ≥ 𝑎
Calculation of A:
According to normalization condition, the total probability that the particle is somewhere
𝑎 𝑎
in the box must be unity.∫0 𝑝𝑥 𝑑𝑥 = ∫0 |𝜓𝑛 |2dx=1
From equation (10)
𝑎
𝑛𝜋𝑥
∫ 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = 1
𝑎
0
𝑎1 2𝜋𝑛𝑥
𝐴2 ∫0 2 [ 1 − cos 𝑎
] 𝑑𝑥 = 1
 𝐴2 𝑎 2𝜋𝑛𝑥 𝑎
[𝑥− 𝑠𝑖𝑛 ] =1
2 2𝜋𝑛 𝑎 0
The second term of the integrand expression becomes zero at both the limits.
𝐴2
[𝑎] = 1
2
2
𝐴 = √𝑎

2 𝑛𝜋𝑥
Therefore the wave function is𝜓𝑛 = √𝑎 𝑠𝑖𝑛 ---------------- (10)
𝑎

Fig. Energy level diagram corresponding to the normalized wave functions of the particle [7]
Therefore, the particle in the box can have discrete values of energy, these energies are
quantized. Note that the particle cannot have zero energy. The normalized wave function ψ 1, ψ2,
ψ3,.. etc., is given by Eqn. (12) is plotted in figure. The values corresponding to each energy value
En is called as Eigen value and the corresponding wave function is called Eigen function.
 FREE ELECTRON THEORY OF SOLIDS
Free Electron Theory:
In solids, electrons in outer most orbits of atoms determine its electrical properties. Electron
theory is applicable to all solids, both metals and non-metals. In addition, it explains the electrical,
thermal and magnetic properties of solids. The structure and properties of solids are explained
employing their electronic structure by the electron theory of solids.
It has been developed in three main stages:
1. Classical free electron theory
2. Quantum Free Electron Theory.
3. Zone Theory.
Classical free electron theory:
The first theory was developed by Drude & Lorentz in 1900. According to this theory,
metal contains free electrons which are responsible for the electrical conductivity and metals obey
the laws of classical mechanics.
Quantum Free Electron Theory:
In 1928 Sommerfield developed the quantum free electron theory. According to
Sommerfield, the free electrons move with a constant potential. This theory obeys quantum laws.
Zone Theory:
Bloch introduced the band theory in 1928. According to this theory, free electrons move in
a periodic potential provided by the lattice. This theory is also called “Band Theory of Solids”. It
gives complete informational study of electrons.
Classical free electron theory:
Even though the classical free electron theory is the first theory developed to explain the
electrical conduction of metals, it has many practical applications. The advantages and
disadvantages of the classical free electron theory are as follows:
Advantages:
It explains the electrical conductivity and thermal conductivity of metals.
1) It verifies ohm’s law.
2) It is used to explain the optical properties of metals.
 3) Metal composed of atoms in which electrons revolve around the nucleus are many states
available for occupation. If the density of states is zero, no states can be occupied at that
energy level.
4) The valence electrons are freely moving about the whole volume of the metals like the
molecules of perfect gas in a container
5) The free electrons moves in random directions and collide with either positive ions or other
free electrons. Collision is independent of charges and is elastic in nature
6) The movements of free electrons obey the laws of classical kinetic theory of gases
7) Potential field remains constant throughout the lattice.
8) In metals, there are large numbers of free electrons moving freely within the metal i.e. the
free electrons or valence electrons are free to move in the metal like gaseous molecules,
because nuclei occupy only 15% metal space and the remaining 85% space is available for
the electrons to move.
Drawbacks:
1) It fails to explain the electric specific heat and the specific heat capacity of metals.
2) It fails to explain superconducting properties of metals.
3) It fails to explain new phenomena like photoelectric effect, Compton effect, black –
4) Body radiation, etc.
5) It fails to explain Electrical conductivity (perfectly) of semiconductors or insulators.
6) The classical free electron model predicts the incorrect temperature dependence of
7) It fails to give a correct mathematical expression for thermal conductivity.
8) Ferromagnetism couldn’t be explained by this theory.
9) Susceptibility has greater theoretical value than the experimental value.
Quantum free electron theory:
In order to remove the failures of classical free electron theory, Somerfield proposed
quantum free electron theory in 1928, based on the quantum concepts.
According to this theory, the electrons in a metal move in a constant potential. He derived
an expression for electron energies by using Schrodinger’s wave equation and De-Broglie concept
of matter waves. He treated the problem quantum mechanically using Fermi– Dirac statistics.
Important assumptions:
1) The potential of an electron is uniform or constant within the crystal.
2) The electrons possess wave nature.
3) The allowed energy levels of an electron are quantized.
4) The electrons have freedom to move within the crystal itself and they are restricted from
leaving crystal due to potential barrier at its surface.
5) The free electrons obey Fermi – Dirac statistics.
Merits of quantum free electron theory:
It explains the electrical conductivity, thermal conductivity and specific heat capacity
of metals, photoelectric effect, Compton effect etc.
Demerits of quantum free electron theory:
1) It fails to provide the distinction between metals, semiconductors and insulators.
2) Fails to explain the positive value of Hall co- efficient and some transport properties of
metals.

Bloch’s Theorem
According to free electron model, a conduction electron in metal experiences constant
potential. But in real crystal, there exists a periodic arrangement of positively charged ions through
which the electrons move. As a consequence, the potential experienced by electrons is not constant
but it varies with the periodicity of the lattice. In zone theory, as per Bloch, potential energy of
electrons considered as varying potential with respect to lattice constant ‘a’.

Fig: Variation of potential energy in a periodic lattice. [8]

Let us consider the picture of the lattice in only one dimension, i.e., only an array of ionic
cores along x-axis. If we plot the potential energy of a conduction electron as a position in the
lattice, the variation of potential energy is as shown in figure. The potential is minimum at the
positive ion sites and maximum between the two ions.
The one dimension Schrodinger equation corresponding to this potential can be written as,
𝑑2 𝜓 2𝑚(𝐸 − 𝑉)
+ 𝜓(𝑥) = 0
𝑑𝑥 2 ħ2
The periodic potential V(x) may be defined by means of the lattice constant ‘a’ as
V(x) = V(x+a)
Bloch considered the solution of the Schrodinger’s equations as,
 Ψ(𝑥) = 𝑒±𝑖𝐾𝑥 𝑈(𝑥)

This equation is known as Bloch function.

UK (x) is periodic with the periodicity of the crystal lattice. The free electron wave is
modulated by function UK(x) which is periodic with the periodicity of the crystal lattice. The free
electron wave is modulated by periodic function UK(x).

Kronig-Penney model:
According to free electron theory, the potential of electron inside a crystal is uniform.
According to Kronig-Penny model, the electrons have variable potential energy due to presence of
immobile lattice ions in crystals and hence potential inside a crystal is not uniform. The variation
of potential energy in a one dimensional lattice is shown in fig.

Fig: Variation in periodic potential of electron moving in a lattice. [8]

The potential of an electron at the positive ion site is zero and it is maximum in between
two ions. Thus between any two ions we get the same variations of potential energy curves and
they are periodic in nature. The periodic potential is given by V(x) and V(x + a), where a is the
lattice constant. To study the behaviour of electron in such varying potential fields, Kronig and
Penny modified the above curves as rectangular square potential wells which shown in figure.

Fig: Approximation of periodic potentials. [8]

 Let the width of the potential well and potential barrier be ‘a’ and ‘b’ respectively. Let
the PE of an electron be V = o in the well, and the barrier be ‘Vo’ the periodically of potential is
(a + b).
The energies and wave functions of electron associated with this model can be calculated
by solving time-independent one dimensional Schrödinger’s wave equation for the two regions I
& II.

The Schrödinger wave equation for the two regions can be written as,
𝑑2 𝜓 2𝑚𝐸
Region – I: + 𝜓(𝑥) = 0 for 0 < x < a …… (1)
𝑑𝑥 2 ħ2
𝑑2 𝜓 2𝑚(𝐸−𝑉0 )
Region-II: 𝑑𝑥 2 + 𝜓(𝑥) = 0 for –b < x <0 …..(2)
ħ2

Let us assume that the energy E of the electrons under considerations is less than V0,
𝑑2 𝜓 2𝑚(𝑉0 −𝐸)
− 𝜓(𝑥) = 0 ……… (3)
𝑑𝑥 2 ħ2

2𝑚𝐸 2𝑚(𝑉0 −𝐸)

Let 𝛼 2 = 𝛽2 =
ħ2 ħ2
𝑑2 𝜓
Region – I: + 𝛼 2 𝜓(𝑥) = 0 for 0< x<a …… (4)
𝑑𝑥 2
𝑑2 𝜓
Region-II: − 𝛽 2 𝜓(𝑥) = 0 for –b < x < 0 ……. (5)
𝑑𝑥 2

The Bloch theorem states that the solution of wave equation for a periodic potential will
be of the form of a plane wave modulated with the periodicity of the lattice of the form.
𝜓(𝑥) = 𝑒𝑥𝑝±𝑖𝑘𝑥 𝑈𝑘 (𝑥)….. (6)
Where 𝑈𝑘 (𝑥) is the modulating function with periodicity (a+b)
After solving (4) and (5) eqns using the modulating wave functions, we get 2nd order differential
equations in U1 and U2.
Upon solving those equations further, we will get values for U1 and U2 with unknown
constants. To find out those constants, we need to solve a 4*4 determinant, which leads us to the
following equation.
𝑚𝑉0
𝛽𝑏 𝑠𝑖𝑛𝛼𝑎 +𝑐𝑜𝑠 𝑐𝑜𝑠 𝛼𝑎 =𝑐𝑜𝑠 𝑐𝑜𝑠 𝑘𝑎
ħ2 𝛼𝛽

𝑚𝑉0 𝑎𝑏
Let potential barrier strength 𝑃 = ħ2
 𝑃
𝑠𝑖𝑛 𝑠𝑖𝑛 𝛼𝑎 + 𝑐𝑜𝑠𝛼𝑎 = 𝑐𝑜𝑠𝑘𝑎
𝛼𝑎

𝑷
Fig: Plot of 𝜶𝒂 𝒔𝒊𝒏 𝒔𝒊𝒏 𝜶𝒂 + 𝒄𝒐𝒔𝜶𝒂 Vs 𝜶𝒂 [8]

The permitted values of energy are shown as shaded portions. This gives rise to the
concept of ranges of permitted values of α (which indirectly signifies the allowed energy) for the
electron moving in periodic potentials.

Conclusions:
1. The motion of electrons in a periodic lattice is characterized by the bands of allowed energy
separated by forbidden regions.
2. As the value of α increase the width of the allowed energy bands also increases and the
width of the forbidden band decreases.
3. If the potential barrier strength P is large, the allowed bands become narrower and
forbidden bands become wider.

Case i): P → ∞ allowed band reduces to a single energy level.

P→∞

………+1……………………

αa

………-1 …………………….
When P → ∞ then 𝑠𝑖𝑛𝛼𝑎 = 0

𝑛𝜋 𝑛2 𝜋 2
𝛼𝑎 = 𝑛𝜋 𝛼= 𝛼2 =
𝑎 𝑎2

But α2 = 2 m E / ħ2
2𝑚𝐸 𝑛2 𝜋 2
= 2
ħ2 𝑎

𝑛2 𝜋 2 ħ2
𝐸=
2𝑚𝑎2

𝑛2 ℎ2
𝐸=
8𝑚𝑎2

Case ii): P→ 0 all the values of αa are allowed.

𝑐𝑜𝑠 𝛼𝑎 = 𝑐𝑜𝑠 𝑘𝑎

α2 = k2

2𝑚𝐸
But 𝑘 2 = ħ2

ħ2 𝑘 2 𝑃2 1
𝐸= = = 𝑚𝑣 2
2𝑚 2𝑚 2

This implies that all the electrons are completely free to move in the crystal without any
constraints, which establishes the classical free electron theory. Hence, all the energies are allowed
to the electrons.
Origin of Energy bands in Solids
The band theory of solids explains the formation of energy bands and determines whether
a solid is a conductor, semiconductor or insulator.
The existence of continuous bands of allowed energies can be understood starting with the
atomic scale. The electrons of a single isolated atom occupy atomic orbitals, which form a discrete
set of energy levels.
When two identical atoms are brought closer, the outermost orbits of these atoms overlap
and interact. When the wave functions of the electrons of different atoms begin to overlap
considerably, the energy levels corresponding to those wave functions split.
If more atoms are brought together more levels are formed and for a solid of N atoms, each
of the energy levels of an atom splits into N energy levels. These energy levels are so close that
they form an almost continuous band. The width of the band depends upon the degree of overlap
of electrons of adjacent atoms and is largest for the outermost atomic electrons.
As a result of the finite width of the energy bands, gaps are essentially leftover between
the bands called forbidden energy gap.
The electrons first occupy the lower energy levels (and are of no importance) then the
electrons in the higher energy levels are of important to explain electrical properties of solids and
these are called valence band and conduction band.

Fig: Formation of Energy bands and band structure in Solids. [9]

Valence band:
A band occupied by valence electrons and is responsible for electrical, thermal and optical
properties of solids and it is filled at 0K.
Conduction band:
A band corresponding to outer most orbit is called conduction band and is the highest
energy band and it is completely empty at 0K.

The forbidden energy gap between valence band conduction band is known as the energy
band gap. Solids are classified in to conductors, semiconductors and insulators, based on the
energy gap between valence and conduction bands.

Classification of Solids:

Fig: Band structure of insulators, semiconductors and conductors. [10]

Conductors:

In this kind of materials, there is no forbidden gap between the valence band and
conduction band. It is observed that the valence band overlaps with the conduction band in metals
as shown in figure. There are sufficient numbers of free electrons, available for electrical
conduction and due to the overlapping of the two bands there is an easy transition of electrons
from one band to another band takes place, and there no chance for the presence of holes.
Resistivity of conductors is very small and it is very few milli ohm meters.(Ω m ).

Examples: All metals (Na, Mg, Al, Cu, Ni Cu, Ag, Li, Ar etc)
Semiconductors:

In semiconductors, there is a band gap exists between the valence band and conduction
band and it is very less and it is the order of -1 to 2 eV are known as semiconductors. It will conduct
electricity partially at normal conditions. The electrical resistivity values are 0.5 to 103 ohm meter.
Due to thermal vibrations within the solid, some electrons gain enough energy to overcome the
band gap (or barrier) and behave as conduction electrons. Conductivity exists here due to
electronics and holes.

Examples: Silicon, Germanium, Ga As.

Insulators:

In insulators, the width of forbidden energy gap between the valence band and conduction
band is very large. Due to large energy gap, electrons cannot jump from V.B to C.B. Energy gap
is of the order of ~10 eV and higher than semiconductors. Resistivity values of insulators are 107
to 1012 ohm-m. Electrons are tightly bound to the nucleus, no valence electrons are available.

Examples: Wood, rubber, glass.

References

1. A text book of Applied Physics by Dr. T V S Arun Murthy and Dr. M N Avadhanulu.
2. http://hyperphysics.phy-astr.gsu.edu/hbase/wien.html
3. Haldolaarachchige, Neel & Hettiarachchilage, Kalani. (2021). A Set of Virtual
Experiments of Fluids, Waves, Thermodynamics, Optics, and Modern Physics for Virtual
Teaching of Introductory Physics.
4. A text book of ‘Concepts of Modern Physics’ by Arthur Beiser.
5. https://www.mphysicstutorial.com/2021/09/davisson-and-germer-experiment.html?m=1
6. https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook
_Maps/Supplemental_Modules_%28Physical_and_Theoretical_Chemistry%29/Quantum
_Mechanics/05.5%3A_Particle_in_Boxes/Particle_in_a_1-Dimensional_box
7. https://homework.study.com/explanation/consider-an-electron-in-a-1d-box-a-leq-x-leq-a-
x-1-nm-plot-the-wavefunction-as-a-function-of-x-for-n-1-2-3-4.html
8. https://www.scribd.com/document/484692519/kronig-penney
9. https://en.wikipedia.org/wiki/Band_gap
10. Gardecka, Aleksandra. (2016). Synthesis and characterisation of niobium doped TiO2
semiconducting materials.