Module-2

PRINCIPLES OF QUANTUM MECHANICS & ELECTRON THEORY

Introduction: In the beginning of 19thcenturaty, the study of energy distribution in the spectrum of
black body radiation become insoluble. Classical as well as Newtonian mechanics failed to explain
it. Hence in 1900 Max Plank explained the spectrum of blackbody radiation with a new theory
called ‘Quantum Theory’.
In Greek Quantum means ‘discreate’ or ‘integral’ or ‘whole’. From 1901 onwards, Quantum
theory become a major part of physics to explained a number of problems like Bohr’s theory and
Hydrogen spectrum etc.,
Waves and Particles:
Universe is mainly made up of two components namely 1.Matter 2. Energy. Each of them is
normally conserved but Einstein showed that mass and energy are mutually convertible under
certain conditions.
A particle has definite mass and occupies a particular point. When the force is applied on it,
it moves in the force direction and it can be physically seen. Characteristics of particles are mass
(m), velocity (v), momentum (p), energy (E) etc.,. The characteristics of a wave are wavelength (λ),
frequency (υ), wave velocity (ω), amplitude (A), phase (Φ), intensity (I) etc.,
As per above facts, radiation exhibits duel nature. The experiments photoelectric effect,
Compton effect says that the radiation like visible light, X-rays, UV etc., exhibits particle nature,
where as experiments like intereference, diffraction says it exhibits wave nature. Hence it can be
concluded that radiation is exhibiting dual nature. i.e., wave nature as well as particle nature. But it
is not possible to exhibits both wave nature and particle nature at a time.
Dual Nature of Matter – de Broglie’s Hypothesis of matter waves:
In 1924, Louis de-Broglie of France put forward a hypothesis which states that ‘Nature loves
symmetry, if the radiation behaves as a particle under some situations and as wave in certain
situations, then matter also exhibits both types of nature i. e., particle and wave called dual nature.
The waves associated with matter are called matter waves.
Based on Plank’s theory of radiation, the energy of a photon is given by E = hυ
hc
E= ------ (1)

where ‘h’ is plank’s constant, ‘c’ is velocity of light, ‘λ’ is wavelength
According to Einstein’s mass-energy relation E = mc2 ------- (2)
 where ‘m’ is mass of photon
hc
From Eq. (1) & (2) mc2 =


h h
λ= → λ= where ‘p’ is momentum of photon
mc p
Applying de-Broglie’s hypothesis to particle: Let an electron of charge ‘e’, mass ‘m’ moving with
velocity ‘v’ in presence of potential ‘V’ then wavelength associated with electron is

h h
λ= → λ= ------- (3)
mv p
If ‘E’ is the energy of the electron in potential field (or) electric field ‘V’ then
E = eV -------- (4)
1
The kinetic energy of the electron E = mv 2 --------- (5)
2
1
From Eq. (4) & (5) eV = mv 2
2
1 2 2
meV = m v
2
m2v2 = 2meV → p2 = 2meV

p= 2meV --------- (6)

 The wavelength ‘λ’associated with the electron moving with velocity ‘v’ is
h h
  --------- (7)
2meV 2mE
Substituting the values of plank’s constant h=6.625 × 10 -34Js
Mass of electron m=9.1 × 10-31Kg
Charge of electron e=1.6 × 10-19C
12.26  10 10 12.26 A
We get    
V V
It shows the wavelength associated with an electron in the presence of potential difference ‘V’.
Characteristics of matter waves
1. Def: The waves that are associated with a moving particle of mass ’m’ are called matter waves.
The wavelength ‘λ’ of matter waves is given by
h h
λ= 
mv p
2. Lighter is the particle, greater is the wave length
3. Lesser the velocity of the particle, longer the wavelength associated with it
4. v = 0 then λ = ∞ , this shows that matter wave is associated with moving particles.
5. Matter waves are produced by any particle in motion. They are independent of the charge of
the particle. Hence they are different from electromagnetic waves which are produced by
charged particles only
6. The amplitude of the matter waves gives the probability of finding the particle at a particular
time and region

c2
7. The velocity of the matter waves always greater than the velocity of light ω =
v
8. No single phenomenon exhibits both particle nature and wave nature at a time.
Davisson and Germer’s experiment:
According to the concept of wave nature of matter fast moving electrons behave like
a wave.
Construction: Davisson and Germer accelerated the electrons from a hot tungsten
filament F by maintaining a steady potential difference between F and the plate P.
The electrons emerge through a fine opening O in the plate and fall normally on the
surface of a nickel crystal N. The intensity of scattered electrons is measured in all
directions by using Faraday cylinder C. The collector C is capable of rotation about
on the axis passing through the point of incidence of the electrons on the crystal N. A
retarding potential is maintained between them so that only fast-moving electrons
coming from the electron gun may enter inside it. The secondary electrons if any,
generated at the surface of nickel are stopped by the retarding potential. Thus the
galvanometer connected to Faraday cylinder C shows defection due to electrons from
the electron gun only.
Working: The Faraday cylinder was moved over the circular scale and for a given
accelerating voltage V, the scattering curve was drawn. For an electron accelerated by
54V applied, an electron beam incident normal to the crystal surface, the pronounced
s attering direction was found to be 50 o. The surface rows of atoms act like the rulings
of a diffraction grating, producing the first order spectrum of 54V electrons at θ=50 o.
Applying Bragg’s law 2d sinθ=nλ
2 x 0.909 x 10-10 x sin(90-25) = 1λ
Λ = 1.648 Å
12.26
According to de-Broglie electron wave 𝜆 = = 1.668Å
√54

The above values are in good agreement, it confirms the de-Broglie concept of matter
waves.
Schrodinger time independent wave equation:
Based on de-Broglie’s idea of matter waves, Schrodinger in 1926 developed a wave
equation for the moving particle. According to him, let a particle of mass ‘m’ moving with a
velocity ‘v’ is associated with a group of waves (along x-axis). Let ‘Ψ’ be the wave function of the
particle. Let us consider a simple form of progressive wave represented by the equation

  o Sint  kx ------ (1)

Where   x, t  and Ψo=amplitude

Differentiating Eq. (1) w.r.t. ‘x’ twice partially is

  o Cost  kx k 
x
  2
  o Sin t  kxk 2 
x 2

 2
 k 2 ( from Eq. (1))
x 2

 2
 k 2  0 ------ (2)
x 2

2
Where k is propagation constant =


 2 4 2
 2  0 ------ (3)
x 2 
The above equation is differential form of the classical wave equation
h
We know the de-Broglie’s wavelength expression  ------ (4)
mv
Substituting Eq. (4) in Eq. (3)
 2 4 2 m 2 v 2
  0 ------ (5)
x 2 h2
The total energy of the particle ‘E’ is the sum of its kinetic energy ‘K’ and potential energy ‘V’
E =K+V ------ (6)
1
And K = mv 2 ------ (7)
2
1
E= mv 2 + V
2
1
E-V = mv 2
2
m2 v2 = 2m(E-V) ------ (8)
substituting Eq. (8) in Eq. (5)
 2 4 2 .2mE  V 
  0
x 2 h2
 2 8 2 mE  V 
  0 ------ (9)
x 2 h2
h h
In Quantum mechanics the value occurs most frequently   using this notation
2 2

 2 2mE  V 
Eq. (9) becomes   0 ------ (10)
x 2 2
The above equation represents one dimensional Schrodinger time independent wave equation,
when it is extended to 3-dimensional wave
 2  2  2 2mE  V 
 2  2   0 ------ (11)
x 2 y z 2

2 2 2
Laplacian operator 2   
x 2 y 2 z 2
2 m E  V 
Eq. (11) can be written as  2   0 ------ (12)
2
This is Schrodinger wave equation and time factor doesn’t appear.
Hence it is time independent wave equation
Physical significance of wave function (Ψ):
1. Wave function gives the information about the particle behavior statistically
2. Ψ is a complex quantity and individually it does not have any meaning

3.     is real and positive, is called probability density function

2

 
2
4. For a given volume it is given by dv

 dx  1 is called normalized condition

2
5.

6. Wave function (Ψ) is a mathematical tool used in quantum mechanics.

7. It can tell the probability of the position of the particle at a time, but it can not predict the
exact location of particle at that time.
Fermi-Dirac distribution and its dependence of temperature:
The electron is indistinguishable particle hence it is called as Fermi particle. In absence of
electric field electron present in metal move randomly and behaves like a electron gas.

Let us consider a metallic crystal, it has free electrons posses different energies. Each
electron possesses quantized energy states. These electrons obey pauli’s exclusion principle. At
absolute zero of temperature the free electrons occupy different energy levels continuously without
any vacancy in between the filled states. This can be understood by dropping the free electrons of a
metal one by one into the potential well. The first electron dropped would occupy the lowest
available energy Eo and the next electron also occupy same energy level. The third electron would
occupy the next energy level i.e., E1 and so on because of pauli’s exclusion principle. If the metal
contains N number of electrons, they will be distributed in the N/2 levels and the higher energy
levels will be completely empty (Fig. 1).
Fermi levelThe highest filled level, which seperates the filled and empty levels at absolute zero (0
K) is known as Fermi level and the energy correspond to the fermi level is called Fermi energy.
As the temperature of metals increased from 0K to T K , the electron present bellow E F regions
takes thermal energy and moved to higher energy level, where as electrons present in the lower
energy level will not take thermal energy because they will not find vacant electron states.
The probability of a particular quantum state at energy E is filled with an electron is given
by Fermi-Dirac distribution function is given by
1
F(E)=
 E  EF 
1  exp  i 
 KT 
Where F(E) is probability of occupation of electron in particular energy
K is Boltzmann constant
Ei is energy of the ith state
EF is energy of the Fermi level
The plot of F(E) Vs E for the above equation shown in Fig. 2. From the figure the following
properties are observed.
 E  EF 
Case (i) Let T= 0 K for Ei<EF ,exp  i  = 0 so that F(E)=1
 KT 
This means all the energy states below E F are filled
 E  EF 
forEi> EF, exp  i =∞ so that F(E)=0
 KT 
This means, all the energy states above E F are empty
Case (ii) Let T > 0 K and Ei = EF then F(E) = ½
Thus Fermi level is the energy level for which the probability of occupation is ½ or 50% at
any temperature.