1

UNIT-2
ELECTRON THEORY OF METALS

INTRODUCTION:
In metals the valence electrons are loosely bound to their individual atoms. They move
randomly in different directions and are called free electrons. Hence, the valence
electrons of the atoms become the conductors of electricity in metals and they are
known as conduction electrons
♣ The electron theory of solids explains the structure and properties of solids. The theory
is applicable to all solids (all metals and non metals). It explains the electrical, thermal
and magnetic properties of solids. The theory has been developed in three main stages.
♣ The Classical free electron theory: This theory developed by LORENTZ & DRUDE in
1900. According to this theory the free electrons of the metals obey the classical
mechanics.
♣ The Quantum free electron theory: SOMMERFELD developed this theory during
1928. According to this theory the free electrons obey quantum laws such that the
wave nature of electrons is taken into account.
♣ The Band theory or Zone theory: In 1928 BLOCH started this theory in which
electrons move in a periodic field provided by the lattice. The concept of hole, origin of
band gap and effective mass of electrons are the special features of this band theory.
PROPERTIES OF THE METALS:
♣ Metals have high electrical conductivity σ.
♣ Metals obey ohms law i.e. the current flowing along a wire is proportional to the p.d
between the ends of the wire. V=iR
♣ If l is length and A is area of cross section of the wire then its resistance is given by
l
R=ρ Where ρ is called resistivity of the material.
A
♣ Ohm‟s law can also be expressed in terms of current density (J) and electric field
strength is given by J =σ E Where σ = is the conductivity

♣ Good electrical conductors are also good thermal conductors. According to

Wiedemann Franz law = constant

where K is thermal conductivity of the metal

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 2
CLASSICAL FREE ELECTRON THEORY: (or) Salient features of Classical freee
electron theory:
LORENTZ AND DRUDE Proposed a theory comparing the electrons with the
orientations of the gas molecules in space. So this is also known as free electron gas
model
Postulates:-
♣ The valence electron of atoms are free to
move in the metals like the gas molecules
in a container.
♣ In the absent of electric field the electrons
move randomly in all possible directions
and the net current is zero.
♣ While moving, the electrons suffer
collisions among themselves. All the
collisions are elastic.
♣ Between any two collisions, the electrons
move with uniform velocity.
♣ Applying kinetic theory to the electron gas, the root mean square velocity of the

electrons are given by Vrms=

♣ The electron speeds are distributed according to Maxwell Boltzmann distribution

law.
♣ The electrostatic force of attraction between positive ion cores and free electrons,
the electrostatic force of repulsion between the electrons is neglected.
♣ The free electrons are confined to the metal due to surface potential.
♣ In the presence of electric field, the free electrons are accelerated in a direction
opposite to the direction of the electric field
♣ The electrons acquires velocity due to application of external electric field is known as
„drift velocity „ (Vd)
DERIVATION OF OHM’S LAW BASED ON FREE ELECTRON THEORY :-

♣ Suppose E is the potential difference applied across a conductor of length L and

cross sectional area „A‟
♣ Let Vd is the average drift velocity and n is the electron density (no. of electrons per
unit volume).
♣ Therfore current density J = -neVd -------->(1)

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 3
♣ The electric field force acting on the electron is given by „-eE‟ and the damping force
Vd
due to collisions taken as m

Vd
♣ At steady state m = -eE

♣ Substituting Vd = from equ -----> (1) in

equ ---> (2) we get

ne 2
[ = -eE J= E  (3)
m
ne 2 ne 2
♣ metal is constant and is known as conductivity „σ‟ ... σ =
m m
♣ Ohm‟s law can also be stated as J = σE
MEAN FREE PATH; -
♣ In metals free electrons are moving in all directions with various speeds. While
moving they collide with other electrons. During collision both the direction and
velocity change.
♣ The electrons followed Zig-Zag paths between collisions. “ The distance travelled by
an electron between any two successive collisions is called „free path‟
♣ The mean of their free paths is called the „mean free path‟. The mean time between
two successive collisions is called collision time c.

♣ The mean free path is given by  =Vrms  c

Where Vrms is the root – mean –
square velocity.
DRIFT VELOCITY :-
♣ In the absence of electric field , the electrons move at random. As a result , the net
current is zero
♣ When electric field is applied , the electrons move in a direction opposite to direction
of electric field.
♣ Due to this field, the electrons gets acceleration. But due to collisions, there will be a
retarding force proportional to the velocity of electrons
♣ A steady state is reached when the retarding force is equal to the applied electric
field force.This steady state velocity is called drift velocity.
Expression: Consider a conductor of length l and cross sectional area A. The entire
charge of the conductor is given by q = Alne

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 4
♣ Current i= =

♣ Current density J= = =

♣ We know that velocity = =

J=neVd Vd=

Note: The drift velocity increases with current and decreases with electron density.
RELAXATION TIME AND MOBILITY:
♣ When electric field is applied between the ends of a conductor a steady state is
reached and electrons acquire drift velocity.
♣ Now if the electric field is switched off, the drift velocity decreases exponentially as
shown in fig.
♣ Suppose vd is drift velocity at t=0
Vd(t) is drift velocity after t sec.
t
Vd(t) = vd e 
Def: Relaxation time is defined as the time in
1
Which the drift velocity falls to
e
of its initial value.
MOBILITY (  ): At steady state, the retarding force
Due to electric field to be equal i.e.,
vd eE
m = -eE  v d = -
 m
vd e
The drift velocity per unit electric field is called mobility. Thus  = =-
E m
EXPRESSION FOR CONDUCTIVITY IN TERMS OF RELAXATION TIME:
Conductivity: It is reciprocal of the resistivity which measures the ability of conducting
electricity through the metals.
Relaxation time: Relaxation time is defined as the time in which the drift velocity falls
1
to of its initial value.
e
♣ As per the electron gas model, the electrons motion is completely random due to
collisions. In the presence of electric field, electrons get accelerated in a single
direction.

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 5
♣ But this is opposed by the damping forces due to collisions. These collisions mainly
between electrons and positive ion cores. This process is called “electron-lattice
scattering”.
♣ when we apply the Potential difference across the metal, the current density „j‟ is
given by J = neVd------(1)
♣ The electric field force acting on a free electron is F = eE -----(2)
♣ According to Newton‟s second law, F = ma -----(3)
♣ since the damping force balances the driving force then from (2) and (3),

eE v eE eE
ma=eE  a =  d =  vd = -----(4)
m  m m
eE ne 2
substituting equation –(4) in equation ----(1), we get j = ne ( )  j= E
m m
ne 2
comparing this equation with ohm‟s law j = σE, we have  =
m

RELATION BETWEEN CONDUCTIVITY AND MOBILITY:

Vd eE
We know that mobility   and Vd =
E m
eE
m e ne 2  e 
Therefore  = = and  = = ne  
E m m m
  = ne 
RELATION BETWEEN CONDUCTIVITY AND MEAN FREE PATH:

 ne 2 ne 2  3k B T
We have   and  =  = but we know v rms =
v rms m mvrms m

ne 2 
 =
3mk B T

SUCCESS OF CLASSICAL FREE ELECTRON THEORY:

♣ It verifies Ohm’s law
♣ It explains the electrical and thermal conductivities of metals.
♣ It derives Wiedemann-Franz law.
♣ It explains Optical properties of metals.
FAILURES (0r) DRAWBACKS OF CLASSICAL FREE ELECTRON THEORY:
♣ Specific Heat: Def: The amount of energy required to raise the temperature of the
system through 1K is called specific heat of the system.

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 6
At a Temp TK, If a molar substance is taken, the total Kinetic energy of the system
3
can be U = N A K BT
2
dU 3 3
CV =  N A K B = X 6.023X1023X1.38X10-23 = 12.46 JK-1
dT 2 2
This value is 100% greater than the experimental value.
3k B T
♠ Mean Free Path: we know that mean free path  =Vrms  c ----- (1) where v rms =
m
At any temperature T,  can be calculated by ----- (1).
But this value is disagreeing with the experimental value.
k
♠ Wiedemann-Franz law: According to this law = constant = L -----(1)
T
2
3 k 
But according to Drude‟s theory L =  B  ------(2)
2 e 
But the calculated values of L from equations (1) and (2) are not coincide.
♠ The phenomenon such as photo electric effect, Compton effect and black body
radiation could not be explained by this theory.
♠ Electrical conductivity of semiconductors or insulators could not be explained using
this theory.
♠ Ferromagnetism could not be explained.
♠ The theoretical value of paramagnetic susceptibility is greater than the experimental
value.
QUANTUM FREE ELECTRON THEORY:
♣ Sommerfeld proposed the quantum free electron theory
♣ A conduction electron free to move inside the crystal but will not come out of metal
because infinite potential present at the surface.
♣ The electrons are trapped in a potential well.

♣ The free electrons can go into different energy levels by following pauli‟s exclusion
principle. This states that “no two electrons in an atom can have the same set of
quantum numbers”.
♣ The motion of free electrons is associated with a wave called matter wave
♣ The electrons will have only discrete energy levels. We know that according to
Quantum mechanical concept
n2h2
En=
8mL2

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 7
♣ Sommerfeld employed the FERMI-DIRAC statistics to describe the distribution of
electrons among different possible energy levels.
♣ Among different energy states, many states are degenerate i.e. several combinations
of quantum numbers with the same energy.
Ex:- (1,1,2), (1,2,1),(2,1,1) all these states have the same energy value.

DISTINGUISH BETWEEN CLASSICAL AND QUANTUM THEORY: (or) DISTINGUISH

BETWEEN LORENTZ DRUDE THEORY AND SOMMERFELD THEORY:

CLASSICAL THEORY QUANTUM THEORY

1. It is proposed by Lorentz-Drude.
2. This theory is applicable to macroscopic
particles such as atoms or molecules.
3. The valence electrons are loosely bound
in the atom should obey the classical
mechanical laws.
4. In the absence of electric field the
electrons move randomly and hence net
current is zero.
5. while moving electrons suffering
collisions among themselves. All
collisions are elastic.
6. Between any two collisions, the
electrons move with uniform velocity..
1. It is proposed by Sommerfeld.
2. This theory is applicable to
microscopic particles such as
electrons.
3. The free electrons obey quantum
laws such that wave nature of
electrons is taken into account.
4. A conduction electron free to move
inside the crystal but will not come
out of the crystal because infinite
potential at the surface.
5. The electrons are trapped in a
constant potential.
6. The free electrons can go into
different energy levels by following
Pauli‟s exclusion principle.

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 8

7. The motion of free electrons is

7. In the presence of electric field, the free
associated with a wave called matter
electrons are accelerated in a direction
wave.
opposite to electric field.
8. Sommerfeld employed the FERMI-
8. The electrons acquires velocity due to
DIRAC statistics
application electric field known as ‟drift
9. According to quantum theory
velocity‟.
n2h2
. 9. The root mean square velocity of the En=
8mL2
electrons are given by Vrms=

FERMI-DIRAC DISTRIBUTION:
♣ According to quantum theory each electron of a metal posses quantized energy
n2h2
states according to the equation En=
8mL2
♣ The electrons are distributed among these energy levels according to pauli‟s
exclusion principle. This allows a maximum of 2 electrons in any sub energy level
with their spins opposite to each other.
♣ The pair of electrons occupy the lowest energy level. The next pair goes to the next
energy level.
♣ This process goes on until all the electrons in the metal occupy all their positions.
N
♣ If there are N electrons, they will accommodate Energy Levels.
2
♣ According to quantum free electron theory, at absolute zero of temperature all the
free electrons occupy different energy levels.
♣ The highest filled level that separates the filled and empty levels at zero Kelvin is
known as the FERMI ENERGY LEVEL. The energy corresponding to this level is
called the FERMI ENERGY.
♣ The probability F(E) of an electron occupying an energy level E is given by FERMI

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 9
DIRAC distribution function as
1
F(E)= ------------(1)
E  EF
1  exp( )
K BT

Where EF is called Fermi energy and F(E) is called Fermi function.

♣ A graph is plotted between F(E) and E at different temperatures T1K and T2K and
so on
At T=0K for E <EF , F(E)=1
i.e. all energy states below EF are filled.
At T=0K for E >EF, F(E)=0
i.e. all energy states above EF are empty.
With increase of temperature, the Fermi function
plot shows deviation as shown in the figure.
♣ At T>0K, E=EF
1
 F(E)=
2

1
FERMI LEVEL is that energy level for which the probability of occupation is at any
2
temperature above 0K .
FERMI ENERGY:-It is the energy of the state at which the probability of electron
1
occupation is at any temperature above 0K.
2
EFFECT OF TEMPERATURE ON FERMI-DIRAC DISTRIBUTION:-
OR
VARIATION OF FERMI-DIRAC DISTRIBUTION WITH TEMPERATURE:-
According to Fermi dirac distribution the probability of an electron
occupying an energy level E is given by
1
F(E)=
E  EF
1  exp( )
K BT

Where EF is called Fermi energy and

F(E) is called Fermi function.
When T>0K and
1
for E<EF  F(E) <1 (but > )
2

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 10
1
E>EF  F(E) >0 (but < )
2
1
E=EF  F(E)=
2
♣ As the temperature increases, more electrons jump into the levels above EF by leaving
vacancies in their energy levels. This can be shown in the above figure.
♣ Thus when T>0K, some levels below EF are not completely filled up and some levels
above EF are not completely empty.
♣ The electrons in the levels above EF and holes below EF are responsible of conduction
in semi conductors.
♣ But the metals are good conductors even at room temperature. If the temperature is
raised, the resistance of the metal increases due to more collisions.
♣ When temperature increases it is observed that Fermi energy level EF (T) decreases.
That means only a small fraction of electrons are effected by the temperature. This
point explains the SPECIFIC HEAT PROBLEM of metal bfbcb s.
FERMI ENERGY AND ITS EXPRESSION:
Def: The Fermi Energy is the energy of the highest occupied quantum state in a system
of electrons at absolute temperature
 The temperature at which electrons possess energy equal to Fermi energy is called
EF
Fermi temperature. We know that KTF = EF  TF =
K
 The velocity of an electron having energy equal to Fermi energy is called Fermi

1 2EF
velocity. We can write EF = mVF2  VF =
2 m
Expression: The product of Fermi Dirac distribution function and density of states gives
the number of electrons per unit volume.
EF

i.e., n =  F ( E ) D( E )dE
0
--------- (1

3
  8m  2 1
where D(E) is density of states and its value is   E 2
and
2  h2 
1
F(E) = At T=0K for E <EF , F(E)=1 then equ---(1) becomes
E  EF
1  exp( )
K BT

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 11
EF
  8m  2  E

3 3 E 3 3
  8m    8m 
EF 2 2 F 2

1 1
 n=  2  h 2  E 2 dE =  2 
 2h   E 2
dE =  2
2h   3 
0 0
 2 0
3 2
  8m  2 3  3n  3
h2
 n=   EF 2
 EF   
2  h2    8m
3
NOTE: Average kinetic energy of free electron gas at 0K is Eav = EF
5
SUCCESS OF QUANTUM FREE ELECTRON THEORY:
This theory has successfully explained the following facts.
 According to classical theory, the specific heat value observed is very large.
According to Quantum free electron theory, only a small percentage of conduction
electrons are receiving thermal energy, the specific heat value become very small.
Acc to this theory, CV = 10-4RT, which is close to experimental value.
 The electrical conductivity obtained is also in good agreement with experiment
values.
 Mean free path explained successfully.
ELECTRON SCATTERING AND RESISTANCE:-
OR
Sources Of Electrical Resistance (Or) Origin Of Electrical Resistance:.
ELECTRICAL RESISTIVITY:
♣ At room temperature, all the materials possess electrical resistance. A measure of
materials ability to oppose the flow of electric current is known as Electrical
resistivity.
♣ It is usually given at 00c or 200c and it is formally known as specific resistance and it
is denoted by  . We know that  t   0 (1  t )

♣ Consider a conductor of length l, area of cross section A and having a resistance R

RA
then the resistivity of that conductor is given by   Units: ohm-m
l
♣ The various sources of electrical resistance are electron scattering, presence of
impurities, crystal defects, thermal vibrations and Pressure on the materials.
Presence Of Impurities: It introduces electrical resistance in a metallic substance. When
the impurity concentration is more, the resistivity increases.
Crystal Defects:- Any small deviation from the perfection is sufficient to produce changes
in the properties of metals. These imperfections are the main sources of electrical
resistance.

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi

 12
♣ The resistance change is generally given by MATTHIESSEN’S rule i.e.
 total =  ph +  impurity --------- (1)

Where  ph is temperature dependent resistivity due to thermal vibrations of the lattice.

 impurity is due to scattering of electrons by impurity atoms.

m m
♣ We can write    -------- (2)
ne  ph
2
ne 2 i

THERMAL VIBRATIONS:-
♣ At Very low temperatures, the amplitude of vibrations small and hence the scattering
of electrons by lattice ions also becomes less.  ph becomes larger. Therefore    i .

♣ At low temperatures, the resistivity is proportional to fifth power of absolute

temperature.   T 5
♣ as the temperature increases, the thermal vibrations of electrons increase and the
relaxation time decreases. Hence the resistivity of the materials increases.
♣ Where as at high Temperatures the resistivity is linearly proportional to absolute
temperature.  T

Note: Near absolute 0K, some materials show zero resistivity known as
Superconductivity.
♣ The variation of resistivity with temperature is shown in the figure.
At 0K,  has a small constant value. As the temperature increases,  increases slowly
the beginning and later it comes linear.
♣ The resistivity is inversely proportional to Pressure
1
ie.,  
P

Venkat Name of the Faculty: Mr D Pavan Kumar, Ms B Bhargavi