Classical free electron theory

Concept of electron:
According to classical theory all metals are good conductors of heat and electricity as they
contain large number of free electrons. These electrons are loosely bound to their respective
atoms. While forming a solid, large numbers of atoms are joined so that boundaries of
neighbouring atoms slightly overlap on each other. Due to thermal energy these loosely
bound electrons get detached from the atoms and move randomly throughout the metal but
cannot escape from the metal, unless external voltage is applied. These electrons are called
free electrons. When external voltage is applied to the metal, electrons flow opposite to the
direction of applied electric field which constitutes an electric current and hence free
electrons are also called as conduction electrons.

The atoms of a metal become ion core after losing electrons. The boundaries of ion of an
atom are called as ion core. The arrangement of ions over the lattice of the metal is known as
lattice core. Lattice core is in a state of thermal vibration about their mean position. During
motion these electrons collide with other lattice ions.
Assumptions of classical free electron theory
To account for large electrical conductivity in metals Drude proposed a theory and
later it was extended by Lorentz. Hence this theory is called Drude Lorentz theory. It is
based on classical theory and it is also called as classical free electron theory.
This theory is based on following assumptions
(a) A metal is imagined to be made up 3-dimensional array of ion cores. Free electrons move
in between the ions. Such free moving electrons cause electrical conduction under an
applied field and hence referred to as conduction electrons.
(b) The free electrons are equivalent to gas molecules and they are assumed to obey the laws
of kinetic theory of gases. In the absence of applied electric field, the thermal energy
associated with each electron at temperature T is equivalent to the kinetic energy
associated with the electrons. It is related as
3 1 2
KT = mv th
2 2
Where K is the Boltzmann constant=1.38X10-23JK-1, m=mass and Vth thermal velocity of
the electron.
(c) The ionic potential due to lattice core is considered to be constant throughout the metal
and effect of repulsion between the electrons is negligible.
(d) The electric current in a metal due to an applied field is due to drift of electrons in a
direction opposite to the direction of the field.

1
 (a) Thermal velocity:
A conductor consists of large number of free electrons of about
1029electrons/m3. Due to thermal energy these electrons are
moving in between the ions with a speed of 106m/s and collide
with ion cores of the conductor. After each collision velocity of
the electron becomes zero. There after start moving in random
direction. Thus in the absence of applied electric field, there is a
kind of randomness in the motion of electrons. Though the free
electrons are in motion, the net flow of current is zero or does
not give rise to any current.
“The average velocity with which the free electrons move inside the conductor due to
thermal energy is called thermal velocity”.

b) Drift velocity (vd):

When an electric field is applied, an electric field is developed inside the conductor. As a
result potential difference is developed between the ends of a conductor. The electrons start
moving opposite to the field direction and collide with ion cores. After each collision velocity
of electrons become zero; and again they gain velocity in a fresh direction but always
opposite to the direction of applied electric field. Even though randomness exists; distance
travelled as well as time of collision between the successive collisions is different.
“The average velocity with which electrons move in a conductor under the
influence of applied electric field is called drift velocity”.
The expression for drift velocity.
Consider a conductor of length „L‟ is subjected to an electric field E. In the steady state,
conduction electrons are drifted opposite to the direction of applied electric field. If ‘m’ is
the mass of an electron, ‘vd‟ drift velocity, ‘τ‟ is the mean collision time, and then resistance
force ‘Fr’ offered to its motion is given by
mv
Fr =ma= d
(1)


If ‘e‟ is the charge on the electron, ‘E’ is the electric field, then force experienced by electron
due to applied electric field is F = eE (2)
In the steady state F = Fr
mv
eE= d

eE
The drift velocity is given by vd  
m
(c) Relaxation time (τr) :
In the absence of electric field, the conduction electrons move in random direction, and hence
the probability of finding an electron moving in any given direction is zero.
i.e. Vav = 0

2
When an external field is applied, net positive value
V1av for the average velocity of the conduction
electrons in a direction opposite to the direction of
field; which is equal to the drift velocity i.e
Vav=V1av
If the field is turned off, the average velocity Vav
starts reducing exponentially as shown in the figure
and is according to the equation.

(1)
Time counted from the instant the field is turned off, Relaxation time
If = equation (1) becomes

Hence relaxation time is defined as

1
“The time interval during which drift velocity of electrons reduces to times
e

the maximum value attained by them when applied field is turned off”.
(d) Mean free path (λ):
The average distance travelled by the conduction electrons between two successive collisions
of conduction electrons under the influence of applied electric field is called mean free path.
d) Mean collision time (τ): The average time interval between two consecutive collisions of
an electron with the lattice cores in a conductor under the influence of applied electric field is
called mean collision time.
τ = λ/vth
Where ‘λ’ is the mean free path, v≈vth is velocity same as combined effect of thermal & drift
velocities.

Note: But ½ mvth2=3/2 KT

Failures of classical free electron theory.

Classical free electron theory has failed to explain specific heat, dependence of conductivity
with temperature and dependence of conductivity on electron concentration as follows
(a) Specific heat:
As per classical free electron theory, free electrons in a metal behave as gas molecules and
3
hence the molar specific heat of electrons at constant volume is given by Cv= R
2
Where R is universal gas constant
But experimentally molar specific heat of free electrons in a metal is given by
CV=10-4RT

3
This is not only less than the experimental value but also depends on temperature. Hence
classical free electron theory failed to explain specific heat.
(b) Dependence of electrical conductivity on Temperature:
According to the assumptions of classical free electron theory

√ ---------------------- (1)

The mean collision time ‘τ’ is inversely proportional to the thermal velocity. (vth= )


i.e.

------ ------------------------- (2) From (1)

√
ne 
2

From the expression σ= -------------- (3)

m
  
Substituting for from equation (3) gives
1
σα -----------------------(4)
T
Therefore according to classical theory, electrical conductivity is inversely proportional to the
square root of absolute temperature. But experimentally σ is inversely proportional to the
temperature T.
1
i.e.  cxpt  ----------- (5)
T

Therefore classical theory failed to explain conductivity with temperature.

(c) Dependence of electrical conductivity on electron concentration:
According to classical theory, electrical conductivity is directly proportional to electron
ne 
2

concentration i.e σ =
m
σαn
Thus as n increases conductivity should increase. But it is contrary to the observation.
Consider the data from the following table.

Metals Electron Con.(n) in/m3 Conductivity in Ω-1m-1

Cu 8.45×1028 5.88×107
Ag 5.85×1028 6.3×107
Al 18×1028 3.67×107
Electrical conductivity of aluminium is lesser than Copper (Cu) and Silver (Ag); even though
electron concentration in Al is higher than that of Cu and Ag. Similar observations are made

4
with Cu and Al. Therefore σ α n do not holds good. Hence the classical free electron theory
failed to explain the dependence of σ on electron concentration.

Problems on classical free electron theory

1. Calculate drift velocity and thermal velocity of electrons in a metal of thickness 1mm
across which a potential difference of 1volt is applied at temperature 300K.Compare
this value with thermal velocity of electrons. Given that mobility of electrons is
40cm2/VS.
Solution:
Vd=?, Vth= ?, L=1mm=1X10-3m; V=1volt; T=300K
2 4 2 V 1
  40 cm / VS  40 X 10 m / VS E    1000 V
L 3
1 X 10

Vd  E =40x10-4x1000=4 ms-1 is drift velocity------(1)

  23 
3 KT  3 X 1 . 38 X 10 X 300  5 1
V th    1 . 17 X 10 mS
m   31  ----(2)
 9 . 1 X 10 

Vd 4 5 1
  3 . 14 x 10 ms
5
Vth 1 . 17 x 10

2. A uniform silver wire has a resistivity of 1.54X10-8 ohm-m at room temperature.

across which an electric field of 1 volt/cm is applied. Calculate (i) relaxation time (ii)
drift velocity and (iii) mobility of electrons; assuming that there are 5.8X10-28
electrons per m-3of the metal. (VTU Jun 2010)

Solution:  1.54X10-8 ohm-m; E=1 volt/cm=1volt/1x10-2m=100V/m;

n=5.8X10-28 electrons per m-3; Vd=?   ? ; =?
(i) Relaxation time
2
ne 
 
Consider m

 31
m m 9 . 1 x 10  14
     3 . 985 x 10 S
2 2 8  28  19 2
ne  ne 1 . 54 x 10 x 5 . 8 x 10 ( 1 . 6 x 10 )

(ii) Drift velocity

 19
 eE  1 . 6 x 10 X 100  14 1 1
Vd      31
x 3 . 98 x 10 ms  0 . 699 . ms
 m  9 . 1 x 10

(iii) Mobility of electrons

Vd  E

V  0 . 699 3 2
   d   6 . 99 X 10 m / VS
 E  100

5
3. Calculate mobility of electrons in Copper assuming that each atom contributes one
free electron for conduction. Given resistivity of copper=1.7x10-8 Ω m, atomic
weight=63.54,density=8.96X103kg/m3 and Avogadro number=6.023x1023/mol.
8
Solution:     ?,   1 . 7 X 10  m ;M=63.54; NA=6.023X1023/g mol;
D=8.96X103Kgm-3; number of electrons per atom =n=1
1
No. of conduction electrons/m3=No.of electrons per atom X NAX D AtomicWt

n A XN A XD
n= AtomicWt

23 3
1 x 6 . 025 x 10 x 8 . 96 x 10 25 3
n   8 . 50 x 10 kgm
63 . 54
    ? Using   ne  we get
 1 2 1 1
    4 . 325 m V S
8 25  19
ne 1 . 7 x 10 x 8 . 5 x 10 x 1 . 6 x 10
4. Calculate free electron concentration and hence mobility of electrons in a aluminium
metal assuming that each atom contributes three free electron for conduction. Given
resistivity of Al=2.7x10-8 Ω m, atomic weight=26.98,density=2.7X103kg/m3 and
Avogadro No.=6.023x1023/mol.
8
Solution: n=?     ?,   2 . 7 X 10  m ;M=26.98; NA=6.023X10-23/gmol;
D=2.7X103Kgm-3; number of electrons per atom =n=3
n A XN A XD
(a) n= AtomicWt

23 3
3 x 6 . 025 x 10 x 2 . 7 x 10 26 3
n   1 . 81 x 10 kgm
26 . 98
(b)     ? Using   ne  we get
 1 2 1 1
    1 . 278 m V S
8 26  19
ne 2 . 7 x 10 x 1 . 81 x 10 x 1 . 6 x 10

6
 Quantum free electron theory

Assumptions of quantum free electron theory.

To overcome failures of classical free electron theory (CFET) Sommerfeld in the year 1928,
modified CFET and this theory is called quantum free electron theory.
This theory is based on 3 quantum and 2 classical ideas ; which are called assumptions of
quantum free electron theory .
(Quantum assumptions)
1. The energy values of the conduction electrons are quantized.
2. The filling up of electrons in various allowed energy levels takes place according
to Pauli’s exclusion principle.
3. Distributions of electrons in various energy levels take place according to Fermi-
Dirac statistics and not by Maxwell-Boltzmann statistics.
(Classical assumptions)
4. The electrons travel under a constant potential inside the metal but cannot go
outside the boundary of lattice.
5. The attraction between electrons & lattice ions and the repulsion between the
electrons are ignored.

Question (6): Explain density of states.

In a solid conductor there are large numbers of allowed energy levels. A group of energy
levels placed close to each other is called as energy band. Each energy band consists of a
large number of energy levels. For instance, 1 mm3 volume of a material consists of more
than 1012 energy levels.
“The number of energy levels present in the energy band E between the energy range E
and E+dE per unit volume is known as density of states”
Consider an energy band present between energy interval E1 and E2. Below E1 and above E2
there are large energy levels. The density of energy levels in any band depends on energy
band E and density of states function is denoted by g(E). As E changes g(E) also changes.
If dE is small, it is assumed that g(E) is constant between E and E+dE. Therefore density of
states in the range E and E+dE is denoted by g(E)dE.

1
 3/2 
8 2 Xm
  E 2 dE
i.e. g(E)dE =  h
3 
 

7
Where m=mass of electron g(E) varies with E .Therefore plot of g(E) against E is as
shown in the figure.

Fermi level and Fermi energy:

A metal containing N atoms consists of N allowed energy levels. Filling up of electron
in various energy levels take place according to Pauli’s exclusion principle. Each energy level
can accommodate a maximum of two electrons, one with spin up and the other with spin
down. The first pair of electrons occupy lowest level or ground state. The next pair of
electrons occupies the first excited state; and so on until all the electrons are accommodated.
When all the electrons are accommodated, there is particular energy level below which all the
energy levels are completely filled and that of above is completely empty at 0K.
This is the case when no thermal energy is supplied.
“The energy corresponding to the highest occupied level at absolute zero temperature
(0K) is called the Fermi energy and the energy level is called Fermi level”. It is denoted
by 'Ef

(i) Expression for Fermi energy at 0K is given by

(ii) Expression for Fermi energy at temperature T> 0K is given by

Except at extremely high temperatures, the second term within the brackets is very small
compared to unity. Therefore Ef(T)=Ef(0) i.e. Fermi energy is almost independent of
temperature
Hence at ordinary temperatures; the values of Ef (0) can be taken to be equal to Ef(T)
Fermi temperature:
Fermi temperature is that temperature at which average thermal energy of electrons becomes
equal to the Fermi energy at 0K. i.e kT=Ef(0) therefore

Average thermal energy of metals at 0k is Ef(0)=5 eV

8
 Therefore
At such temperatures metals become liquids. Therefore Tf is only theoretical importance.
Fermi velocity.
Fermi velocity is that velocity of electrons whose kinetic energy equal to Fermi energy at 0K
 2 E f (0) 
1 2  
 E f (0) v f 
i.e mv  m 
2  

What is Fermi factor? Discuss its variation with temperature and energy.
Fermi factor
Fermi factor is the probability of occupying an electron into a given energy level
when the material is in thermal equilibrium.
Probability of energy state with energy E is occupied by electron at a steady
temperature T is given by Fermi factor f(E) and is given by

Where Ef is Fermi energy, K=Boltzmann constant=1.38x10-23 JK-1 and T is temperature in

Kelvin.
The Fermi factor varies with temperature and energyl. Its variation is as shown in the figure
and is discussed as follows
1. Variation of f(E) with temperature T=0K
At T=0K, f(E) is discussed for E < EF and E > EF.
Case (i): At T = 0K and E < EF
E – EF = - ve

f (E) = 1
At T=0K all the energy levels lying below Ef is completely filled.
Case (ii): At T = 0K and E > EF
for E > EF; E – EF = + Ve

9
∴ f (E) = 0
At T=0K all the energy levels lying above Ef are
vacant or unoccupied by electrons. Hence at T=0K
the variation of f(E) for different energy values,
become a step function as shown in the figure

2. Variation of f(E) with temperature at T > OK

At T > OK, f(E) is discussed for E < EF ,E=Ef and E > EF.
Case (i): At T > OK and E < Ef
At ordinary temperatures i.e T> 0K, E – EF = - ve

f(E) = 1
At T> 0K all the energy levels lying far of below Ef is completely filled.
since all the electrons lying far of below Ef. cannot get required energy and hence not excited
above Fermi levels.
But when E approaches to Ef , only some of the electrons lying very close to Fermi level can
absorb energy and get excited above Fermi level. Hence f(E) starts reducing from 1 for
values of E closer to and lesser than Ef as in the figure.
Case (ii): At T >OK and E=Ef
At T > OK and E = Ef

This means 50% of electrons lying at Ef are thermally excited above higher energy levels.
Case (iii): At T > OK and E > Ef
for E > EF; E – EF = + Ve

∴ f (E) = 0
Hence all the energy levels lying above Ef are unoccupied by electrons.

10
 Describe Fermi-Dirac statistics
The number of energy levels per unit volume of the
material in the energy range E & (E+dE) is g(E)dE.
The number of electrons distributed between energy range
E & (E+dE) per unit volume is represented by N (E)dE.
... N(E)dE= The number of energy levels X Fermi factor
N (E) dE = g(E)dE× f(E)

But f(E) and g(E) at a temperature T changes with E; therefore N(E)dE also changes with E.
The plot of N(E) vs E is as shown in the fig.
The plot of N(E)dE against E represents the actual distribution of electrons and The
distribution is known as Fermi–Dirac distribution.

Based on quantum theory derive an expression for electrical conductivity in a

conductor
Consider a conductor of area of cross section „A „across which an electric field is
applied. Let E be the electric field developed inside the conductor. Electrons are drifted
towards positive end of the conductor with drift velocity Vd.. Let m* be the effective mass of
electron.

Current in the conductor is given by  I  nev d A -------------------- (1)

Where n=number of electrons per unit volume, e=charge of electron
Wavelength associated with the electron is given by =
h
P
h
i.e P= where P=momentum of electron

2 2
but k=   
 k
hk
P= --------------------------------------------- (2)
2

Also P=m*Vd------------------------------------------------ (3)

Eqn (3)=Eqn.(4)
hk
=m*Vd
2
hk
Vd= *
-------------------------------- (4)
2 m

Force=Rate of change of momentum

11
 dp d
F=  m * (V d ) ------------------------------------------ (5)  p=m*Vd
dt dt
Force experienced by the electron in the direction of field is given by

F = eE----------------------------------- (6)

Eqn.(6)=Eqn.(5)
d
eE  m * (V d )
dt
d hk m * h dk h dk
Substituting for Vd from eqn.(4) gives eE  m * ( )  
dt 2 m * 2  m * dt 2  dt
dk 2
 eE
dt h
2
On Integration gives k  eE  ---------------------------------- (7)
h
Where =mean collision time
From Ohms law current density J=E where =conductivity of conductor
hk
Substituting for Vd= *
from (4)
2 m
Also on substituting Vd and k,
=
J I nAeV d neV d ne hk
    ( )
*
E E AE E E 2 m

neh  2 
= *
 eE  
2 m E  h 

=
ne

*
m

Describe how quantum free electron theory has been successful in overcoming the
failures of classical free electron theory
Quantum free electron theory has been successful in overcoming failures of classical free
electron theory as follows
(a) Specific heat: According to CFET all conduction electrons are capable of absorbing heat
energy according to Maxwell Boltzmann statistics which results in large specific heat
3
Cv= R
2
But according to quantum free electron theory, only a few of electrons lying very close
to , are capable of absorbing heat energy to get excited into higher energy levels which
results in small value of specific heat.
According to quantum free electron theory, it can be shown that
( ) --------------------------------------------------- (1)
Considering average thermal energy of electrons for a metal = 5 eV

( )

∴ ( )
This is in close agreement with experimental value.

12
b) Dependence of electrical conductivity on Temperature:
Experimentally electrical conductivity  is proportional to and not as given by classical
√
free electron theory.
It is discussed as follows:

Electrical conductivity  = (2)

According to quantum free electron theory  is given by
= ---------------------------- (3)

∴= ( ) --------------------- (4)

For a metal n, e and m are constants. Also according to QFET; Vf are independent of
temperature. Hence only λ & T are variables.
 ( ) ---------------------------- (5)
But λ can vary with temperature. As temperature increases amplitude of vibration of ion
cores increases. The cross sectional area of ion cores which blocks the path is πr2 where „r‟ is
the radius of ion core. As temperature increases πr2 increases; the increase in area of ion core
will decrease mean free path λ, since larger area of cross section can scatter more number of
electrons, it results in reduction in the value of mean free path of electron.
∴λα
∴ ( ) (5)
πr2 proportional to T
∴ ( )
Thus  ( )is correctly explained by quantum free electron theory.
(c) Dependence of Electrical conductivity on electron concentration:
As per quantum free electron theory, electrical conductivity is given

( )
Density of electrons in copper (Cu= 8.45x1028/m3) which is lesser than that of Aluminium
(Al=18x1028/m3); but conductivity of copper is more than aluminium. This can be explained
as follows. The value of n for Cu is 0.469 times that of in aluminium (8.45/18), the value of
λ/vf for copper is about 3.73 times higher than that of aluminium.
The ratio of conductivity of copper to that of aluminium is 1.75; hence conductivity of copper
is more than aluminium.

13
 c n c     v f  8 . 45 3 . 73
    X  1 . 75   c  1 . 75  Al
[Note:  Al n Al  v     18 1
 f c  Al

Problems on classical free electron theory

1. Calculate the probability of an electron occupying an energy level 0.02eV above the
Fermi level and 0.02eV below the Fermi level.
Solution: (a) F(E )= ? for E-Ef=0.02ev=0.02X1.6X10-19J=3.2X10-21J

F(E ) =
23.8% of energy levels lying below Fermi levels are filled and 76.2% of energy levels lying
above Fermi levels are completely empty.
(b) F(E )= ? for E-Ef=-0.02ev=-0.02X1.6X10-19J=-3.2X10-21J

F(E )=
2. Find the temperature at which there is 1% probability that a state with energy 0.5eV
above Fermi energy is occupied. k=1.38x10-23J.
Solution: T=?; E-Ef=0.5ev=0.5X1.6X10-19J=0.8X10-19J;F(E )=1%=0.01

0.01=

14
 T=1261.1K
3. Find the temperature at which there is 1% probability that a state with energy
0.25eV above Fermi energy is occupied. k=1.38x10-23J.

4. Calculate the Fermi velocity and mean free path for the conduction electrons in
Silver, given that its Fermi energy is 5.5eV and the relaxation time for electrons is
3.83x10-14S.
Solution: Vf=?λ=?Ef=5.5ev=5.5x1.6x10-19J=8.8X10-19J;τ=3.83X10-14S
Fermi velocity Ef=1/2mVf2

Fermi velocity ; Vf=

λ = Vf Xτ=1.36X106X3.83X10-14m=5.32x10-8S
5. Fermi level in Silver is 5.5 eV at 0K. Calculate the number of free electrons per unit
volume and the probability of occupancy for electrons with energy 5.6 eV is silver at
the same temperature.
Solution: Ef(0)=5.5eV=5.5x1.6x10-19J=8.811x10-19J, n=?; F(E )=? At E=5.6eV
Fermi energy at 0k is given by

At T=0K,the energy level 5.6 is unoccupied (calculate yourself)

6. Calculate Fermi energy in ev for a metal at 0K, whose density is 10500kg/m3 , atomic
weight is 107.9 and it has 1 conduction electron per atom
Solution: n=?; Ef(0)= ? density D=10500 kg/m3,M=107.9 number of electrons per atom(nA)=1

15
 (a) n= =
(b) Fermi energy at 0K is

7. Fermi level in Silver is 5.5ev.What are the energies for which the probabilities of
occupancy at 300K is (a) 0.99 (b) 0.5 (c) 0.01
Solution: (a) E1=? if F(E1 )= 0.99,given Ef=5.5eV

=0.01

E1-Ef=-4.605x1.38x10-23x300
E1-Ef=-0.119ev
E1 =Ef-0.119ev
E1 =5.5ev-0.119ev
E1 =5.381ev
(b)E2=? if F(E )= 0.5,given Ef=5.5ev

16
(c) E3=? if F(E )= 0.01,given Ef=5.5eV Answer E3=5.6188ev

17