FREE ELECRON THEORY OF METALS

To explain the properties of metals, different theories were put forwarded. One of them is
classical free electron theory.

Classical Free Electron Model (or) Lorentz-Drude Theory:

According to this theory

1. Metal consists of positive ion cores with the valence electrons move freely among these ion
cores. So the valence electrons are responsible for conductivity and they are called free
electrons or conduction electrons

2. The potential field of these positive ion cores is assumed to be constant throughout the metal
and the mutual repulsion among the electrons is neglected.

3. The behaviour of the free electrons moving inside the metal is considered to be similar to that
of atoms or molecules in perfect gas. These free electrons are therefore also referred to as
free electron gas and the theory is named as “free electron gas model”.

4. Since the conduction electrons move in a uniform electrostatic field of ion cores their
potential energy is remains constant and is normally taken as zero. Thus total energy of
conduction electrons is their kinetic energy only.

5. When electric field is applied electrons are accelerated and suffer elastic collisions with the
metal ions which slow down their speed. This gives rise a steady current is proportional to
the voltage applied. This is ohm’s law. (J = σ E this is known as another form of ohm’s law)

6. This theory is used to derive Widemann – Franz law. According to this law

Thermal Conductivity k Thermal Conductivity k

∝ T or = LT (constant)
Electrical Conductivity σ Electrical Conductivity σ

Where L is proportionality constant called Lorentz number.

− −
7. According to this theory mean free path λ of electrons is λ = C τ . Where C is average
velocity of electrons and τ is mean collision time of electrons.

Merits:

1. This theory verifies ohm’s law.

2. This theory explains electrical conductivity and thermal conductivities of metals.
3. This theory explains optical properties of metals such as optical absorption, reflection and
opaque nature of metals etc.
 FREE ELECRON THEORY OF METALS

Demerits or Drawbacks or Limitations:

1. This theory cannot explain why only some crystals are metals some are semiconductors and
others are insulators.
2. Specific heat of electrons: This theory fails to explain heat capacity of conduction electrons.
3
According to this theory specific heat of electron is R . Where R is universal gas constant.
2
But experimental results show that specific heat of electrons is only 0.01R.

3. Specific heat of metals: this theory also fails to explain the specific heat of metals. According
to this theory specific heat of metal is 3R. But experimental results show that specific heat is
4.5R.
4. This theory cannot explain photoelectric effect, Compton Effect and blackbody radiation.
5. Magnetic susceptibility: This theory cannot explain the paramagnetic susceptibility of
conduction electrons.
1
6. According to this theory σ ∝ but experimental results show that σ ∝ T only
T
Relaxation Time ( τ ):

When electrical field is applied electrons attain some velocity. If the field is turned off, the
velocity starts decreasing exponentially.

If <v0> is the average velocity at time t = 0,

<v> = <v0> e-t/τ ---------- (1)

The factor τ is called relaxation time.
When t = τ the above equation becomes
< v0 >
<v> =
e
Thus relaxation time may be defined as the time taken for the drift velocity to
1
decay to of its initial value.
e
Mean Free Path (λ λ ):

When electric field is applied to the metal electrons suffer elastic collisions
to the metal ions. The average distance traveled by an electron between the successive collisions
is called mean free path.
− −
λ = Cτ c where C is average velocity of electrons and τc is mean collision time of
electrons.
 FREE ELECRON THEORY OF METALS

Mean Collision Time(ττc): The average time taken for the electron between the successive
collisions is called mean collision time of electrons.

Drift Velocity (v d ) : when electric field is applied to the metal electrons acquire combined
movement called “drift” and corresponding velocity is called drift velocity.
∴ v d = a τ c -------- (1)
eE
We know F = ma = eE or a =
m
eE
∴ vd = τc ---------- (2)
m
Where τc is mean collision time.

MOBILITY OF ELECTRONS (µ):When electric field is applied to the metal electrons acquire
some velocity is called drift velocity which is directly proportional to the electric field applied.
vd ∝ E or vd = µE

The proportionality constant µ is called mobility of electrons.

Current density of electrons J = ne vd

= neµE

= σE

Where σ =neµ

σ
∴Mobility µ =
ne

RELATION BETWEEN THE RELAXATION TIME AND COLLISION TIME:

τC
τ=
1 − 〈 COSθ 〉

where τ is relaxation time and θ is scattering angle when electron strikes the metal atom.
〈cos θ 〉 is average value of cosθ for all collisions. 1- 〈cos θ 〉 is reduced value of 〈cos θ 〉 in
collision. For isotropic metals 〈cos θ 〉 = 0, τ = τc.

Expression for Conductivity (from classical free electron model):

 FREE ELECRON THEORY OF METALS

According to Kinetic Theory of gases, Kinetic Energy of the gas molecule ∝ Temperature

1 1 3
mv2 ∝ T or mv2 = K B T or
2 2 2

3K B T
v= --------- (1)
m

When the electric field is applied to the metal, electrons experience Lorentz force eE and
acclerates electrons with acceleration ‘a’.

We have, F = ma = eE or

eE
a= --------- (2)
m

eE
The drift velocity v d = aτ = τ ---------- (3)
m

The current density J can be written as

J = ne v d
ne 2τ E
J= -------- (4)
m
Where ‘n’ is electron concentration.
Equation (4) is in the form of J = σE this is ohm’s law.

ne 2τ
Where σ= ------- (5) is electrical conductivity.
m

λ
But τ = , where λ is mean free path of electrons.
v
ne 2 λ
σ=
mv
Substitute the value of ‘v’ from equation (1) into the above equation, we get

ne 2 λ
σ= -------- (6)
3mK B T

From the above equation resistivity ρ ∝ T

Fermi Level:
 FREE ELECRON THEORY OF METALS

At absolute zero all electrons in the metal are occupied up to the

maximum energy level. This maximum energy level is called
Fermi energy level EF.
Above the Fermi level all energy states are empty. Below the
Fermi level all energy states are filled with electrons.
So the Fermi level acts as boundary between the filled levels and
unfilled levels at ok.
As the temperature increases the location of Fermi energy level is
not constant.
The Fermi-Dirac distribution function is
1
F(E) =
 E − EF 
1 + exp 
 K BT 
FERMI ENERGY:
The no. of available electrons per unit volume in metal is given by
EF

n= ∫ F ( E ) Z ( E )dE
0
---------- (1)

where F(E) is probability of occupation of electrons in energy level with energy E

Z(E) is available energy states per unit volume
3
EF 1
1 π  8m  2

∴n= ∫0  2  E 2 dE
 E − EF  2  h 
1 + exp 
 K BT 
In metal at T = 0k, E<EF, F(E) = 1
EF 1
π  8m 
∴n= ∫ 2  h
0
2  E dE

2

1 EF 1
π  8m 
=  E
2  h2 
2
∫E
0
2
dE

EF
 3 
1  
π  8m  E2
=  2 E 2  
2h   3 
 
 2 0
1 3
π  8m 
=   E 2 E F2
3  h2 

− 32
3 3n  8m 
Or E F2 =  
π  h2 
 FREE ELECRON THEORY OF METALS
2 3
 3n  h2
EF =  
π  8m

This is the expression for Fermi energy.

FERMI – DIRAC DISTRIBUTION FUNCTION:

The probability of occupation of a particular energy level E by an electron is given by

1
F(E) =
 E − EF 
1 + exp 
 K BT 

Case (i): At T = 0k and for E < EF

1 1
F(E) = −∞
= =1
1+ e 1+ 0

Case (ii): At T = 0k and for E > EF

1 1
F(E) = ∞
= =0
1+ e ∞

This means at absolute zero all energy states below Fermi level EF are occupied and all energy
states above are empty. That is from figure Fermi distribution function is a step function. Thus at
0k the Fermi level EF represents the highest filled energy level.

1
Cas (iii): At T > 0K and E = EF, F(E) =
2

This means EF lies between the filled levels and empty

levels.

Case4: For T > 0k but less than melting point of the

metal, the distribution function losses its step character.
The probability of occupation F(E) decreases
gradually from 1 to 0 near EF.
This indicates some of the states below EF are empty
while some others above are empty

SOMMERFELD QUANTUM FREE ELECTRON MODEL:

According to Sommerfeld
1. Electrons obey the laws of quantum mechanics instead of classical mechanics.
 FREE ELECRON THEORY OF METALS

2. The energy of the electron is discrete, i.e. energy is quantized.

3. Electrons near to the Fermi surface only are responsible to the electrical conductivity.
4. Potential field inside the metal is uniform. Later a correction made in this postulate that field
experienced by a moving free electron varies periodically with the periodicity of the crystal.
5. The energy is distributed among the electrons is according to Fermi – Dirac statics

The electron can be represented by a vector from the origin to a

specific location in 3-dimensional velocity space or k space as
2π
shown in figure. Here ‘k’ is wave vector of electron, k =
λ
According to quantum mechanics the momentum of the electron
can be written as

mv = h k or
hk
v= -------- (1)
m
dv dk
Acceleration a = m = h = eE or
dt dt
eE
dk = dt -------- (2)
h
Integrating the above equation between the limits t = 0 to t = t,
t
eE
∫ dk =
0
h ∫ dt
eE
k(t) – k(0) = t
h
eE
or ∆k = τ ---------- (3) (Q t = τ )
h
Current density J = nev ------ (4)

From equations (1) and (4)

ne h∆k
J= ---------- (5)
m*
From equations (3) and (5)
ne h eE
J= * τ
m h
ne 2τ
J= E This is in the form of J =σE
m*
ne 2τ
Where σ= is electrical conductivity and m* is effective mass of electron.
m*
 FREE ELECRON THEORY OF METALS

Drawbacks:

1. This theory also fails to explain the distinction between metals, semiconductors and insulators.
2. Sommerfeld cannot explain why the shape of the Fermi surface is spherical.

DISTINCTION BETWEEN CLASSICAL FREE ELECTRON MODEL AND QUNATUM

FREE ELECTRON MODEL:
Classical Free Electron Model Quantum Free Electron Model

1. All electrons in the metal are 1. Electrons near to the Fermi Surface are
responsible for electrical conductivity. responsible for electrical conductivity
2. 2.Electrons obey the laws of Maxwell- 2. Electrons obey the laws of Fermi – Dirac
Boltzmann statistics statistics
3. Energy of the electron is continuous 3. Energy of the electron is discrete.
4. Potential energy of the electron is 4. This theory also tells potential of the
constant throughout the metal. electron is constant but later it was modified
that potential of electron varies with the
periodicity of the crystal.
5. This theory cannot explain the specific 5. This theory successfully explains the
heat of electrons and metal. specific heat of electrons and metal.
6. This theory fails to explain mean free 6. This theory explains mean free path and
path and paramagnetic susceptibility of paramagnetic susceptibility of electrons
electrons.
7. Classical theory unable to explain the 7. Quantum theory also failed to explain the
distinction between the metals, distinction between the metals,
semiconductors & insulators. semiconductors & insulators.
8. This model was introduced by Lorentz 8. This model was introduced by Sommerfeld
& Drude