Unit – IV

Quantum Mechanics

Introduction, de-Broglie hypothesis, Heisenberg

uncertainty principle, physical significance of wave
function, postulates of quantum mechanics: operators in
quantum mechanics, eigen values and eigen functions,
expectation value; Schrödinger's time independent wave
equation, particle in a 1D box, Bloch’s theorem
(qualitative), Kronig-Penney model (qualitative): E-k
diagram, effective mass of electron, formation of energy
bands, origin of bandgap, classification of solids, concept
of discrete energy levels and quantum confinement in
nanomaterials.
Introduction:
‘Quantum mechanics describes motion and interaction of
particles at a small scale, where the discrete nature of the
physical work becomes important.’
Waves and Particles:

WAVES:
A wave is nothing but a disturbance that occurs in a
medium, and it is specified by its frequency, wavelength, phase,
amplitude, and intensity.

PARTICLES:
A particle or matter has mass, and it is located at some
definite point, and it is specified by its mass, velocity, momentum,
and energy.
 Wave
character

WAVE–
PARTICLE
DUALITY
Particle
character
de-Broglie hypothesis(1924) and Matter waves

According to de-Broglie hypothesis, any moving particle is

associated with a wave. The waves associated with particles are
known as de-Broglie waves or matter waves.

➢The entire universe consists of matter and radiation(energy)

only.
➢Nature is symmetrical in so many respects, therefore, the two
physical entities viz., matter and energy must be mutually
symmetrical.

He derived an expression for the wavelength of matter waves

on the analogy of radiation.
• According to Planck’s theory of radiation , the energy of photon
is
E = h
c
= h ............(1)

Where ‘c’ is a velocity of light and ‘λ’ is a wave length.
• According to Einstein mass-energy relation
E = mc ......(2)
2

From equation (1)&(2), c

mc 2 = h

h
=
mc
h h
= =
mv p
Where ‘p’ is momentum of the quantum particle, ‘λ’ is de-Broglie
wavelength and ‘m’ is relativistic mass.
 The above relation is called de Broglie’ s matter wave equation.
This equation is applicable to all atomic particles.
de Broglie wavelength associated with Kinetic Energy:
• If ‘E’ is kinetic energy of a particle
1
E = mv 2
2
p2
E=
2m
 p = 2mE

• Hence the de Broglie’s wavelength

h
=
2mE
 de Broglie wavelength associated with electrons:
Let us consider the case of an electron of rest mass m and
charge ‘e’ being accelerated by a potential difference ‘V’ volts.
If ‘v’ is the velocity attained by the electron due to acceleration
1 2
mv = eV
2
2eV
v=
m
h h
but  = =
p mv
h h
=  =
mv 2eV
m
m

• The de Broglie’s wavelength =

h
or  =
12.26 0
A
2meV V
Problems:
1) Calculate the wavelength associated with an electron raise to a potential
1600V(Ans: 0.306A0)
2) Calculate the wavelength associated with an electron with energy
200eV(Ans: 0.0275 nm)
3) Calculate the velocity and kinetic energy of an electron of wavelength
1.66X10-10m.
4) If the kinetic energy of the neutron is 0.025eV. Calculate its de Broglie
wavelength( mass of neutron =1.674X10-27kg).(Ans:0.181nm)
5) An electron is moving under a potential field of 15kV. Calculate the
wavelength of the electron wave.(Ans:0.1A0)
6) Calculate the wavelength of matter wave associated with a neutron whose
kinetic energy is 1.5times the rest mass of electron. (Ans:9.76X10-6m).
7) Calculate the de Broglie wavelength associated with proton moving with
a velocity of 1/10 th velocity of light.(Ans: 1.323X10-14m)
 h
xp 
4
• This relation is universal and holds for all canonically conjugate
physical quantities like
h
1. Angular momentum & angle j  4
2. Time & energy h
tE 
4

Consequences of uncertainty principle:

➢ Explanation for absence of electrons in the nucleus.

➢ Existence of protons and neutrons inside nucleus.
➢ Uncertainty in the frequency of light emitted by an atom.
➢ Energy of an electron in an atom.
 Schrödinger time independent wave equation:
According to de-Broglie’s hypothesis, the particle in motion is
always associated with a wave. To describe the motion of a particle in
terms of its associated wave, Schrödinger derived a wave equation,
which is termed as Schrödinger’s wave equation.
Consider a particle of mass ‘m’ ,moving with velocity ‘v’ is
associated with group of waves, let ‘ψ’ be the wave function of the
particle.
The classical differential equation of a wave motion is given

 2   2
  2
  2
 
= v 2
 +
 x 2 y 2 +  = v 2  2 - - - -(1)
t 2   z 2


The solution of equation(1) is given by

ψ(x)=A sin(ωt-kx) -------(2)
where A is amplitude
k is wave number(= 2π/λ)
Differentiating ‘ ’ partially with respect to ‘ x’ twice

= −kA cos(t − kx)
x
 2
= − k 2
A sin(t − kx)
x 2

= −k 2  ( from eqn (2))

 2
 2 + k 2 = 0 - - - - - -(3)
x
 2 4 2 2
+ 2  = 0 ( k = )
x 2
 
h
According to de - Broglie' s λ =
mv
 2 4 2 m 2 v 2
 2 +  = 0 - - - - - (4)
x h 2
 The total energy E of the particle is the sum of its kinetic energy
and potential energy(V)
1
i.e., E = mv 2 + V
2
 m 2 v 2 = 2m( E − V ) − − − − − (5)
Substituting the equation (5) into equation (4), we get

 2 8 2 m
 + ( E − V ) = 0 - - - - - (6)
x 2
h 2

Now, extending above equation for a three dimensional wave

 2  2  2 8 2 m
 2 + 2 + 2 + 2 ( E − V ) = 0 - - - - - (7)
x y z h
(or )
8 2 m
  +2
2
( E − V ) = 0
h
 (or )

2m h
   + 2 ( E − V ) = 0 (
2
= )
 2

2 2 2
Where  = 2 + 2 + 2 is Laplacian Operator
2

x y z

This is the Schrödinger Time Independent wave

equation.
 Physical significance of the wave function
Max Born in 1926 gave a satisfactory interpretation of the wave
function ‘ψ’ associated with a moving particle.
➢ ‘ψ’ is the wave function and its measures the variation of the
matter waves. Thus, it connects the particles and its associated
wave statistically.
➢ ‘ψ’ is the complex amplitude of the matter wave.
➢ ‘ψ’ must be finite, continuous, and single valued every where.
  
➢ ,
x y
&
z
also, must be finite, continuous and single valued.
➢ The wave function ‘ψ’ is a complex function, it does not have a
direct physical meaning, but when we multiply this with its
complex conjugate ψ* , the product ψ* ψ or | ψ|2 has the physical
meaning.
➢ The wave function Ψ( r, t ) describes the position of a particle
with respect to time.
➢ The probability of finding a particle in a particular volume
is
+

  d = 1
 *

-

where dτ = dx dy dz

i.e., ‘ψ’ must be normalizable.

 Particle in a one dimensional potential box

Consider an electron of mass ‘m’ in an infinitely deep one-

dimensional potential box with a width of a ‘ L’ units in
which potential is constant and zero.

m
V ( x ) = 0,0  x  L
V ( x ) = , x  0 & x  L
V=0

X=0 X=L
 The motion of the electron in one dimensional box can be
described by the Schrödinger's equation.

d 2 2m
2
+ 2 [ E − V ] = 0
dx 
Inside the box the potential V =0

d 2 2m
2
+ 2 [ E ] = 0
dx 
d 2 2m
2
+ k  = 0 → where, , k = 2 E
2 2

dx 

The solution to above equation can be written as

 ( x) = A sin kx + B cos kx − − − −(1)
 Where A,B and k are unknown constants and to
calculate them, it is necessary to apply boundary
conditions.

• When X = 0 then Ψ = 0 i.e. |Ψ|2 = 0 ……. (a)

X = L then Ψ = 0 i.e. |Ψ|2 = 0 …… (b)

• Applying boundary condition ( a ) to equation ( 1 )

A Sin k(0) + B Cos k(0) = 0 → B=0

• Substitute B value in equation (1)

 ( x) = A sin(kx)
 Applying second boundary condition for equation (1)
0 = A sin kL + (0) cos kL
A sin kL = 0
sin kL = 0
kL = n
n
k =
L
Substitute B & k value in equation (1)
(nx)
 ( x) = A sin
L
To calculate unknown constant A, consider normalization condition.
 L

  ( x)
2
Normalization condition dx = 1
0

nx
L

o A sin [ L ]dx = 1
2 2

2nx
L
1
A  [1 − cos[
2
]dx = 1
o
2 L
A2 L 2nx L
[x − sin ]0 = 1
2 2n L
A2
L =1
2

A = 2/ L
 The normalized wave function is
n
 n = 2 / L sin
x
L
2mE k 2 2
k = 2 →E=
2

 2m
2 2
 n   h 
   
L   2 
E=
2m
n h
where,.k = & =
L 2
n2h2
E=
8mL2
The wave functions Ψn and the corresponding energies En which
are called Eigen functions and Eigen values, of the quantum
particle.
Normalized Wave function in three dimensions is given by

n1x n2y n3z

 n = (2 / L ) sin
3
sin sin
L L L

The particle Wave functions & their energy Eigen values

in a one-dimensional square well potential are shown in
figure.
 n2h2
nx En =
 n = 2 / L sin 8mL2
L
E3=9h2 / 8mL2
n =3
L/3 2L / 3

E2=4h2/8mL2
n=2
L/2

√ (2 / L)
E1=h2 / 8mL2
n=1
X=0 L/2 X=L
 Conclusions
1. The three integers n1,n2 and n3 called Quantum numbers are
required to specify completely each energy state.

2. The energy ‘ E ’ depends on the sum of the squares of the

quantum numbers n1, n2 and n3 but not on their individual
values.

3. Several combinations of the three quantum numbers may give

different wave functions, but of the same energy value. Such
states and energy levels are said to be degenerate.
Problems:
1). Find the lowest energy of an electron confined in a box of side
0.1nm each. (Ans: 112.9eV)
2). An electron is bound in one-dimensional box of size 4X10-10m.
What will be its minimum energy?(Ans: 0.346X10-18 joule).
3). An electron is bound in one dimensional infinite well width
1X10-10m. Find the energy values in the ground state and first
two excited states.
(Ans: E1=0.6031X10-17 joule, E2= 2.412X10-17 joule and
E3=5.428X10-17 joule)
• Classical free electron theory:
-It is a macroscopic theory.
-Proposed by Drude and Lorentz in 1900.
-It explains the free electrons in lattice.
-It obeys the laws of Classical Mechanics.
• Quantum free electron theory:
-It is a microscopic theory.
-Proposed by Sommerfeld in 1928.
-It explains that the electrons moves in a constant potential.
-It obeys the Quantum laws.
• The Zone theory:
-Proposed by Bloch in 1928.
-It explain that the electrons moves in a periodic potential.
-It also explain the mechanism of semi conductivity, based
on bands and called ‘Band theory of solids.
Introduction:
• There is variation in resistivity with temperature, especially, in
case of semiconductors.

• The potential experienced by an electron during its motion

through the crystal is periodic, instead of being constant or zero.

• The energy band theory of solids is the basic principle of

semiconductor physics and it is used to explain the differences in
electrical properties between metals, insulators and
semiconductors.

• The concept of discrete allowed electron energies that occur in

a single atom and large number of allowed energies of
electrons are explained by band theory of solids.
 Electron in a periodic potential – Bloch theorem:

• According to Bloch, a one-dimensional lattice consists

of large number of positive ion cores at regular
intervals and the conduction electrons moves freely
throughout the lattice.

• The variation of potential inside the metallic crystal

with the periodicity of the lattice is explained by Bloch
theorem.
 Electron follows spiral path when it moves under varying
Potential and figure is represented below. It experiences zero
Potential at centre of the ion core and maximum potential
between the two ion cores. The motion of the electron through
periodic lattice can be explained by Schrödinger's time
independent equation.
Barrier surface
+ + + +
Vmax
+ + + +

+ + + + +
+ + + +
V=0
+ + + +
One dimensional periodic lattice
with varying potential in a crystal.
Note: At barrier surface V is infinite
•From Schrodinger wave equation, we have
d 2 8 2 m
2
+ 2 [ E − V ( x)] = 0 ------(1)
dx h
Here V(x) is the periodic potential and satisfy the equation
V ( x) = V ( x + a ) -----------(2)
where x is the distance of the electron from any ion core
a is the lattice constant
•Bloch has shown that the one dimensional
solution of the Schrodinger equation
 k ( x) = U k ( x) exp(ikx) --------(3)
where U k ( x) is periodic function
• The free electron wave is modulated by the periodic function
Uk(x). Now, let us consider a linear chain of atoms of length ‘L’ in
one dimensional with ‘N’ number of atoms in the chain (where ‘N’
is even), then
Uk(x)= Uk(x+Na) ---------(4)
From equation (3)&(4), we have
Ψk(x+Na)= Uk(x+Na)exp[iK(x+Na)]
=exp(iKNa) Uk(x) exp(ikx)
Therefore, Ψk(x+Na)=Ψk(x)exp(iKNa) ------(5) is called Bloch
condition
Taking the complex conjugate of the above equation, we get
Ψk*(x+Na) = Ψk*(x)exp(-iKNa) -----(6)
Multiplying the equation (5)&(6), we get
Ψk(x+Na) Ψk*(x+Na) = Ψk(x) Ψk*(x)
 i.e., the electron is not localized around any particular atom and
the probability of finding the electron is same throughout the
crystal.
Hence from equation (5),

exp(ikNa)=1
i.e., kNa=2Πn
therefore, k=2Πn/Na=2Πn/L
where L is the length of the chain of atoms
and ‘n’ is the integer, which can take values 0,1,2,3,…
If we consider that N=2n, then k=Π/a, this represents the
boundary and is called the first Brillouin zone.
The allowed values of ‘k’ with in the first zone is equal to ‘N’.
 Kronig–Penney model
According to Kronig Penny model, the potential of the
solid varies periodically with the periodicity of space
lattice “a” which is nothing but inter atomic spacing.

Region –II V(x)=V0 (x)

Region –I V(x)=0

0 a
• It is assumed that the potential energy of the electron is zero
near the nucleus of the positive ion in the lattice and
maximum when it is half way between the adjacent nuclei as
shown in Figure above..
i.e,
V ( x ) = o.... for ,.0  x  a
and
V ( x ) = V0 .. for ,. − b  x  0

• The Schrodinger wave equations for the two regions can be

written as
d 2 8 2 m
2
+ 2
E = 0 - - - -(1) (region - I)
dx h
d 2 8 2 m
2
+ 2
[ E − V0 ( x)] = 0 − − − ( 2)(region − II )
dx h
 Let assume that the energy ‘E’ of the electron under
consideration is less than V0. Let us put
8 2 m
 =
2
2
E
h
8 2 m
and  =
2
(V0 ( x) − E )
h2
d 2
 +  2
 = 0.....(3)
dx 2

d 2
and 2
−  2
 = 0.....( 4)
dx

According to Bloch, The solutions of wave

functions Ψ for equations (3) and (4) are of the form
 k ( x) = U k ( x) exp(ikx)........(5)
 Where Uk(x) is the periodicity of the lattice and can be written as
U k ( x) = U k ( x + a) = ..........U k ( x + Na )
The form of Uk(x) depends on the exact nature of the
potential field. As V0 increases the width of the ω
decreases so that the product ‘V0ω’ remains constant.

It turns out that solutions are possible only for energies

given by the relation is

P
cos ka = sin a + cos a - - - (6)
a
 4 2 ma
Where P = 2
V0 
h

‘P’ is called scattering power of the potential barrier which is

the measure of strength with which electrons are attracted by the
positive ions.
‘V0ω’ is called barrier strength

8 2 mE
 =
2
= K 2

h2
k 2h2
E =
8 2 m
 P
sin a + cos a
a

+1 +1

a
-1
-1

Un allowed bands Allowed bands

Conclusions :

1. The motion of electrons in a periodic lattice is characterized

by the bands of allowed energy separated by forbidden
regions.
sin a
P + cos a
a

+1

0
a
-1
2. As the value of αa increases, the width of allowed energy
bands also increases and the width of the forbidden bands
decreases.

3. If ‘V0ω’ is large ,i.e. if ‘P’ is large ,the function described by

the right-hand side of the equation crosses +1 and -1 region
as shown in figure.. Thus, the allowed bands become
narrower and forbidden bands become wider.
As P → infinite, the allowed energy bands are compressed
into energy levels and a line spectrum is resulted.
p→
sin a = 0
p→ a =  n
 n
 =
a
0 a 8 2
mE
As we know that  2 =
h2
 n 2 8 2 mE
( ) =
a h2
n2h2
E=
8ma 2

It clearly explains that the particle (electron) is confined to One

dimensional infinitely deep square well potential box , Where we
can find discrete energies ( En = n2E1).
 i.e., cos a = cos ka
4. If P tends to zero No energy levels exist:
all energies are allowed for the electrons. n
 =k =
a
2 = k2
p→0
2mE
k = = 2
2 2


2 2
E = ( )k
a 2m
h 2 2 2
E = ( 2 )( )
8 m 
h2 1
E=( ) 2
All energies are possible for electron 2m 
2 2 2
and the energy spectrum is continuous h p p 1 2
E=( ) 2 = = mv
2m h 2m 2
Note:
Kronig-Penny model and Bloch theorem yields the following
results:

➢ There are allowed energy bands separated by forbidden

regions or band gaps.

➢ The electronic energy functions E(k) are periodic in the wave

vector k.
Brillouin zones:
The Brillouin zone is a representation of permissive values of k of the
electrons in one, two or three dimensions. Thus, the energy spectrum
of an electron moving in the presence of a periodic potential field is
divided into allowed zones and forbidden zones
When a parabola representing the energy of a free electron is
compared with the energy of an electron in a periodic field as shown in
Figure, it is clear that the discontinuities in the parabola occur at values
of k given by n
k =
a
Since k is wave vector
n n
k = =
 a
2a = n

Which reflects Bragg’s condition for normal incidence.

Therefore
n
the electron suffers Bragg’s reflection at the values
k=
a which results in discontinuities in the E-k curve.
 E

For free Energy gap

electron Allowed
bands

Energy gap

−
3
a
−
2
a
−

a
0 
a
2
a
3
a k
 n
note : k =  is the boundary condition for
a
electron motion and at these values , the energy is discontinuous
 
 The region between - and + is called first Brillouin zone
a a
 2  2
 the region between - , − and + ,+ is called second
a a a a
Brillouin zone.
llly the other Brillouin zones are explained for electron motion.
Effective mass of an electron:
• When an electron in a periodic potential of lattice is
accelerated by an electric field or magnetic field, then
the mass of the electron is called effective mass (m*)
and which is different from the mass ‘m’ of the electron
in free space.
• Let us consider an electron of charge ‘e’ and mass ‘m’
moving inside a crystal lattice of electric field E.
• Therefore, the electrical force on the electron F=eE
But F= m*a -----(1)
m*a=eE
Therefore, acceleration a=eE/m*----(2)
 Considering the free electron as a wave packet, the group velocity
‘vg’ corresponding to the particle’s velocity can be written as

d dv
vg = = 2 (  = 2v)
dk dk
2 dE
= ( E = hv)
h dk
1 dE h
= (  = )
 dk 2
dv g 1 d 2E
But , acceleration a = =
dt  dkdt
1 d 2 E dk
a= 2
− − − − − (3)
 dk dt
Since k = P
dk dp
 = =F
dt dt
dk F
 = − − − − − −(4)
dt 
fromequation (3) & (4), we get
2
1 d E
a= 2 2
F
 dk
2
 F = 2 a − − − − − (5)
d E
dk 2
 comparing equation (1) & (5), we get
2
m = 2
*

d E
dk 2

Thus, the mass of a moving electron in a periodic lattice

(effective mass of electron) is not a constant, but a function of
2
‘k’ and depends on d E2
dk
 E
1).E vs k curve: The mass can be infinite When
d2E/dk2 tends to zero. It can be negative in the
regions marked N,
k0
v 2)V vs. K curve: as the k increases, the velocity
increases, reaching a max. value at k=k0, beyond k0
the vale of v decreases reaching the zero at k = П/a.
The negative values of wave vector exhibit a
similar behavior.
m* 3).Variation of m* with k:
from the curve, the effective mass m* is positive
between –k0 and +k0 and negative at other values
of ‘k’ up to ±П/a. It means that the effective mass
is negative at the top of the band.
fk
Beyond the inflexion point k0, velocity decreases
N N i.e., acceleration is negative. This means that in this
region of ‘k’ the lattice exerts a large retarding
force on electron. In this region of ‘k’ the electron
behaves as a positive charged particle referred to
as a ‘hole’.

/a
-/a 0
 4).Variation of fk with K:

The degree of freedom of an electron is generally defined by

a factor.
2
m m d E
fk =  = 2 { 2 }
m  dk

Here fk is a measure of the extent to which an electron in state k

is free. If m* is large, fk is small , i.e, the particle behaves as a
‘heavy’ particle. When fk = 1 , the electron behaves as a free
electron.
Origin of energy band formation in solids:

• When we consider isolated atom, the electrons are tightly

bound and have discrete, sharp energy levels.

• When two identical atoms are brought closer the outer most
orbits of these atoms overlap and interact.

• 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 levels of energy.

• The levels are so close together that they form an almost

continuous band.

• The width of this band depends on the degree of overlap of

electrons of adjacent atoms and is largest for outer most
atomic electrons.
 E1

E1
E2

E1
E2
E3

N atoms

N energy levels
ΔE
• The energy bands in solids are important in
determining many of physical properties of solids.
The allowed energy bands are
(1) Valance band
(2) Conduction band

• The band corresponding to the outer most orbit is

called conduction band and the inner band is known
as valence band. The gap between these two allowed
bands is called forbidden energy gap.
Classifications of materials into Conductors,
Semiconductors & Insulators:-
In solids the gap between the two outer most allowed
energy bands depends on the equilibrium spacing between the
atoms. This band gap decreases with decreasing of equilibrium
spacing as shown in fig.
 On the basis of values of forbidden ( band ) gap, the
solids are classified into conductors, semiconductors
and insulators.
Conductors(Metals):-

➢ In conductors there is no forbidden gap and both

valence and conduction bands overlaps each other as
shown in figure.

➢The electrons moves freely from valance band to

conduction band.

➢The value of energy gap(Eg) is zero.

Conductors (Metals)
Insulators:-
➢ In case of insulators, the forbidden energy band is very wide as
shown in figure below.
➢ Due to this fact the electrons cannot move from valance band to
conduction band even at high values of energies.
➢ In insulators at 00k , the energy gap(Eg) is of the order of 5eV to
10eV.

Insulators
SEMI CONDUCTORS:

➢ In semi conductors, the forbidden band is very small as shown

in figure.
➢ Ge and Si are the best examples of semiconductors.
➢ Forbidden ( band ) gap(Eg) is of the order of 0.7ev for Ge
&1.1ev for Si.

Semiconductors
Quantum Confinement Effect
At reduced dimensions, they are said to be either a quantum
well, a quantum dot, or a quantum wire.
The physics at these dimensions is entirely different.
Actually, when the size of the grains is reduced to nano-level, then
overlapping of wave function and quantum confinements occurs.
If d is the diameter of the grain size, then the energy goes up
by factor 1/d2
When the dimensions of a potential well or a box concerned
with a particle are reduced to the order of de Broglie wavelength of
electron (within few tens of nanometers), then energy levels of
electrons change.
This effect is called quantum confinement.
The Quantum effects can begin to dominate the behaviour of matter
at the nanoscale - particularly affecting the following properties

[Link]: Spectral shift of optical absorption and fluorescence,

increase in efficiency of semiconductor crystal.

[Link]: Increase in conductivity in ceramics and magnetic

nanocomposites.

[Link] behaviour of materials: Increase in magnetic

coercivity

4. Mechanical properties – increased hardness

5. Chemical properties – increases reactivity

6. Catalytic: Better catalytic efficiency due to high surface area.