UNIT-III

QUANTUM MECHANICS AND ELECTRON THEORY

Basic terms and definitions

Matter waves Wave associated with the motion of a particle (or) Matter waves
are nothing but waves and are usually associated with a moving
quantum particle.
de Broglie hypothesis Matter waves are a central part of the theory of quantum
mechanics, being an example of wave–particle duality. All matter
can exhibit wave-like behaviour. The concept that matter behaves
like a wave was proposed by Louis de Broglie in 1924. It is also
referred to as the de Broglie hypothesis.
Mobility In steady state the drift velocity per unit electric field is called
Mobility.
Relaxation Time The time taken for the drift velocity of an electron to decay 1/e
times of its initial value is called Relaxation Time
Mean collision time The duration between two successive collisions when electron is
in random motion is called Mean collision time
Mean free path The average distance travelled by an electron between two
successive collisions during their random motions is called mean
free path
Drift Velocity When an electric field (E) is applied to the metal electrons
experience force (F) in opposite direction to the applied field. this
force is called Drift Velocity
Merits of Classical free electron 1.It verifies ohm's law 2.It explains the electrical and thermal
conductivities of metals. 3.It derives Weid eman-franz law. 4.It
explains optical properties of metal.
Postulates of Classical free 1. In metals there are large number of free electrons moving freely
electron theory in all possible directions
2. free electrons in the metals are assumed to behave like gas
molecules obeying the kinetic theory of gases
3. In metals electrons move randomly and collide with either +ve
ions or with free electrons all the collisions are elastic (i.e., no lose
of energy)
4. When electron field is applied to the metal the free electrons
accelerated in the opposite direction to the applied field
Drawbacks of Classical free 1.Classical free electron fails to explain the temperature
electron dependence of electrical conductivity
2 .fails to explain specific heat of a solid.
3. fails to explain Wiedemann-franz law that is at lower
temperatures, the ratio of thermal conductivity to electrical
conductivity is proportional to temperature.
4. Electrical conductivity for semiconductors and insulators are not
explained.

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Postulates of quantum free 1 .In a metal the available free electrons are fully responsible for
electron theory electrical conduction.
2. The electrons move in a constant potential inside the metal..
3. Electrons have wave nature, the velocity and energy distribution
of the electron is given by Fermi-Dirac distribution function.
4. The loss of energy due to interaction of the free electron with
the other free electron.
5.Electron’s distributed in various energy levels according to Pauli
Exclusion Principle.

Advantages of Quantum free 1.This theory explains the specific heat capacity of materials.
electron theory 2.This theory explains photo electric effect, Compton Effect and
block body radiation. etc.
3.This theory gives the correct mathematical expression for the
thermal conductivity of metals.

Drawbacks of Quantum free 1.This theory fails to distinguish between metal, semiconductor
electron theory and Insulator.
2.It also fails to explain the positive value of Hall Co-efficient.
3.According to this theory, only two electrons are present in the
Fermi level and they are responsible for conduction which is not
true.

Fermi Level The Fermi Level is the highest energy level which an electron can
occupy at the absolute zero temperature.
Fermi energy The Fermi energy is the energy of the highest level of quantum
state which is occupied by the fermions (like electrons, protons or
neutrons) at the absolute zero temperature.
Sources of electrical resistances 1.Lattice vibration
2.Impurities
3.Structural imperfection
Energy band Energy bands consisting of a large number of closely spaced
energy levels exist
Energy Gap The gap between conduction band and valence band. It is denoted
by Eg. Energy gap value is different for different solids.
Energy gap in Metals-0 ev
Energy gap in semiconductors  1ev
Energy gap in Insulators -  5ev

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Concepts:

Quantum Mechanics:

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Matter wave Properties:

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Physical significance of  :
 The wave function 𝛙 enables all possible information about the particle. 𝛙 is a complex
quantity and has no direct physical meaning. It is only a mathematical tool in order to
represent the variable physical quantities in quantum mechanics.
 2. Born suggested that, the value of wave function associated with a moving particle at the
position co-ordinates (x,y,z) in space, and at the time instant ‘t’ is related in finding the particle
at certain location and certain period of time ‘t’.
 3. If 𝛙 represents the probability of finding the particle, then it can have two cases.
Case 1: certainty of its Presence: +ve probability
Case 2: certainty of its absence: - ve probability, but –ve probability is meaningless,
Hence the wave function 𝛙 is complex number and is of the form a+ib
 4. Even though 𝛙 has no physical meaning, the square of its absolute magnitude |𝛙2| gives a
definite meaning and is obtained by multiplying the complex number with its complex
conjugate then |𝛙2| represents the probability density ‘p’ of locating the particle at a place at
a given instant of time. And has real and positive solutions.
𝛙 (𝐱,𝐲,𝐳,𝐭)=𝐚+𝐢𝐛
𝛙∗(𝐱,𝐲,𝐳,𝐭)=𝐚−𝐢𝐛 𝐩= 𝛙𝛙∗=|𝛙2|=𝑎2+𝑏2 𝑎𝑠 𝑖2=−1
Where ‘P’ is called the probability density of the wave function
 5.If the particle is moving in a volume ‘V’, then the probability of finding the particle in a
volume element dv, surrounding the point x,y,z and at instant ‘t’ is Pdv
∫|𝛙2|𝑑𝑣=1 𝑖𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑒𝑙 𝑖𝑠 𝑝𝑟𝑒𝑠𝑒𝑛𝑡
∫|𝛙2|𝑑𝑣 = 0 if particle does not exist
This is called normalization condition

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Particle in one dimensional Potential Box:

 The wave nature of a moving particle leads to some remarkable consequences when the
particle is restricted to a certain region of space instead of being able to move freely .i.e when
a particle bounces back and forth between the walls of a box.
 The wave nature of a moving particle leads to some remarkable consequences when the
particle is restricted to a certain region of space instead of being able to move freely .i.e when
a particle bounces back and forth between the walls of a box.
 The Schrodinger wave equation will be applied to study the motion of a particle in 1-D box to
show how quantum numbers, discrete values of energy and zero point energy arise.
 From a wave point of view, a particle trapped in a box is like a standing wave in a string
stretched between the box’s walls.
 Consider a particle of mass ‘m’ moving freely along x- axis and is confined between x=0 and x=
a by infinitely two hard walls, so that the particle has no chance of penetrating them and
bouncing back and forth between the walls of a 1-D box.
 If the particle does not lose energy when it collides with such walls, then the total energy
remains constant.
 This box can be represented by a potential well of width ‘a’, where V is uniform inside the box
throughout the length ‘a’ i.e V= 0 inside the box or convenience and with potential walls of
infinite height at x=0 and x=a, so that the PE ‘V’ of a particle is infinitely high V=∞ on both
sides of the box.

The boundary condition are

𝑣(𝑥)=0 ,𝜓(𝑥)=1𝑤ℎ𝑒𝑛 0<𝑥<𝑎…. (1)
𝑣(𝑥)=∞ ,𝜓(𝑥)=0𝑤ℎ𝑒𝑛 0≥𝑥≥𝑎… (2)
Where 𝜓(𝑥) is the probability of finding the particle.
The Schrodinger wave equation for the particle in the potential well can be written as
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