BPHYEE102 Applied Physics for EEE Stream

Module II - Quantum Free

Electron Theory
Syllabus
Failure of classical free electron theory, Assumptions, Fermi energy, Fermi fac-
tor, Variation of Fermi factor with temperature and energy, Density of states
(with derivation), Expression for Fermi Energy at zero Kelvin, Merits of Quan-
tum free electron theory, Numerical problems.

Definitions
• Drift velocity (vd ): It is the average velocity of the electron in the direction
opposite to the applied electric field.
• Mean free path (λ): It is the average distance travelled by the electron
between two successive collision with lattice.
• Mean collision time (τ ): It is the average time interval between the two
successive collision of electron with lattice. It is also known as relaxation time.
• Mobility (µ): The magnitude of the drift velocity acquired by the electrons
vd
per unit electric field µ = .
E

Drawbacks of classical theory of free electron

• The specific heat for conduction electrons at constant volume for monovalent
3
elements is theoretically given by Cv = R = 1.5R, where R is universal gas
2
constant. But the experimentally it is found to be 0.015R a small value.
• It has been experimentally observed that for metals the electrical conductivity
1
σexpt ∝ .
T
But the average kinetic energy of an electron at a temperature ‘T’ due to
classical free electron theory assumption is given by
1 2 3
mv = kT
2 2

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Applied Physics for EEE Stream BPHYEE102
r
3kT
v=
m
√
v∝ T
Since, the mean collision time τ is inversely proportional to the thermal velocity,
we can write
1
τ∝
v
we can write
1
τ∝√
T
But conductivity, σ is given by

ne2 τ
σ=
m

σ∝τ

1
σ∝√
T
Experimentally observed dependency of conductivity on temperature is not in
agreement with theoretical.

ne2 τ
• σ= ⇒ σ ∝ n. But the conductivity of monovalent element like Cu is
m
greater than the bivalent element like Zn.

Element n(m)−3 σ (Ωm)−1

Cu 8.5 × 1028 5.88 × 107
Zn 11.310 × 1028 1.09 × 107

• The resistivity of metal is given by

m
ρ=
ne2 τ

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BPHYEE102 Applied Physics for EEE Stream

The resistivity of copper at 20◦ is 1.69 × 10−8 Ωm and density of free electrons
n = 8.5 × 1028 /m3 . Thus,
m
τ= 2
ne ρ

9.1 × 10−31
τ= = 2.47 × 10−14 s
8.5 × 10 × (1.6 × 10 ) × 1.69 × 10
28 −19 2 −8

But
λ
τ=
c̄
where c̄ is random velocity.
λ = τ × c̄ = 2.47 × 10−14 × 1.154 × 105 = 2.85 nm

Mean free path as experimentally measured is ten times greater than the values
predicted by classical theory.

Postulates of quantum free electron theory

• The energy values of free electrons are quantized.
• The energy distribution of free electrons occur as per Pauli’s exclusion principle.
• The electrons move under constant potentials inside the metal. They stay
confined to the boundaries.
• The attraction between the electron as well as repulsion between the electrons
are neglected.

Fermi energy
It is the energy of the highest occupied level by an electron at zero kelvin and the
corresponding energy level is known as fermi level.

E
DE
EF

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Fermi Factor
During the thermal excitation the electrons absorb energy and move into higher
states above fermi energy. The energy distribution takes place as per Fermi-Dirac
Statistics. The probability of occupation of energy state by a single electron at a
steady temperature T is called Fermi Factor. It is given by,

1
f (E) = E−EF
e kT +1
where, EF is the fermi energy and is a constant for the particular system, E -
energy of the level whose occupancy is being considered, k - Boltzmann constant.
At T = 0 K,
• For E < EF at T = 0 K, f (E) = 1. All energy states upto fermi level are
occupied.
• For E > EF at T = 0 K, f (E) = 0. All energy states above fermi level are
empty.
At ordinary temperature, T > 0 K
• For E < EF , f (E) < 1, the probability of occupancy of an electron decreases
from 1.
1
• For E = EF , f (E) = . The probability of occupancy of electron is 50%.
2
1
• For E > EF , f (E) < towards 0. The probability of occupancy of electron
2
decreases from 21 towards zero.

Fermi Velocity
It is the velocity of electrons occupying Fermi level. It is given by
1
EF = mvF2
2
r
2EF
vF =
m

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BPHYEE102 Applied Physics for EEE Stream

f(E)
KT T = 0K
1

1/2
T > 0K
E
EF

Density of Energy States

It is defined as the number of energy states per unit volume of metal. Electron
confined in a three dimensional metal is similar to a particle confined in a three
dimensional box whose surfaces have infinite potential. Energy of such an electron
is given by
n2 h 2
E= (1)
8ma2
n2 = n2x + n2y + n2z with nx , ny , nz being energy quantum numbers for electron along x,
y, z directions respectively. m → mass of electron. a → dimension of metal along x,
y and z directions respectively. The number of energy states for a given ‘E’ depends
on the number of combinations of nx , ny , nz .
ny

dn

n E+dE
E
nx

nz

Consider a sphere with of radius n, with axes being nx , ny , nz . Every point with in
the sphere is a combination of nx , ny , nz such that n2 = n2x + n2y + n2z . Each point on
the surface of the sphere represents the energy state. The number of energy states
within the sphere of radius ‘n’ is
 
1 4 3
πn
8 3

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The number of energy states within the sphere of radius ‘n+dn’ is

 
1 4 3
π(n + dn)
8 3
The number of energy states between n and n + dn or in the energy interval dE is
given by,
  
1 4
g(E)dE = π[(n + dn)3 − n3 ] (2)
8 3

π 3
g(E)dE = [n + dn3 + 3n2 dn + 3ndn2 − n3 ] (3)
6
dn is small. Hence dn3 and 3ndn2 are neglected.
π
g(E)dE ≈ (3n2 dn) (4)
6

π
g(E)dE = n(ndn) (5)
2
From(5)
8ma2 E
n2 = (6)
h2

 12
8ma2

1
n= E2 (7)
h2
Differentiating (5)
8ma2
 
dn
2n =
dE h2

8ma2
 
1
dn = dE (8)
2n h2
Substituting (11) and (12) in (9)
" 1 #   
8ma2 2 1 8ma2

1
g(E)dE = E2 dE
h2 2 h2

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BPHYEE102 Applied Physics for EEE Stream

 23
8ma2

π 1
g(E)dE = E 2 dE (9)
4 h2
According to Pauli’s exclusion principle every energy state can accommodate 2 elec-
tron with opposite spin. The number of energy states actually available are,
 32
8ma2

π 1
g(E)dE = 2 × E 2 dE (10)
4 h2

 23
8ma2

π 1
g(E)dE = E 2 dE (11)
2 h2

Density of Energy states for unit volume is given by,

  23
π 8m 1
g(E)dE = E 2 dE (12)
2 h2

Expression for Fermi Energy

The number of electrons in a system with energy E is given as

N (E)dE = g(E)dE × f (E)

At T = 0 K, E < EF , f (E) = 1
Z  π   8ma2  32 Z EF
1
N (E)dE = E 2 dE
2 h2 0
3
 π   8ma2 2 3 EF2
N= E2
2 h2 3 0
3
 π   8ma2  2 3
N= EF 2
3 h 2

The number of electrons per unit volume is

 π   8ma2  32 3
EF 2
N 3 h2
n= =
V V

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Applied Physics for EEE Stream BPHYEE102

Taking V = a3
 π   8m  23 3
n= EF 2
3 h2
 32
h2

3 3n
E =
2
F
π 8m
 32 
h2
 
3n
EF =
π 8m

Merits of quantum theory of free electron

• The small value of specific heat (Cv ) for conduction electron
The minimum energy required for exciting all the free electrons will be EF .
Hence fraction of electrons that will be excited at T = 300K is given by

kT 0.025
= = 0.005 = 0.5%
EF 5

At room temperature less than 1% of valence electrons contribute to the heat

capacity. Each electron may absorb a kinetic energy of the order 23 kT . The
energy associated with a k-mol of the metal will be
  
kT 3
U = NA kT
EF 2

NA k 2
  
3 2
U= T
EF
2
 
dU kT
Cv = = 3NA k
dT EF

with kT = 0.025 eV and EF = 5 eV

Cv = 3R(0.005) = 0.015R

According to quantum theory, only those electrons which are occupying the
energy states close to EF can participate in thermal excitation.

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BPHYEE102 Applied Physics for EEE Stream

• Effect of temperature on σ
According to quantum free electron theory, average velocity of electron changes
very little with temperature. It is almost equal to vF
λ
τ=
VF
Substituting for τ
ne2 λ
σ=
mvF
If the electron moves under periodic potential within the metal then
ne2 λ
σ=
mvF
vF and EF are independent of temperature, but λ depends on temperature.
As temperature increases amplitude of vibration of ion increases. If a is the
amplitude of vibration, then the ions can be considered to be present effectively
in a circular area of cross section πa2 , which blocks the path of the electron
wave irrespective of the direction of approach. Increased scattering results in
reduction in the value of mean free path of electrons.

a2 ∝ T
But
1 1
λ∝ ∝
a 2 T
Since
σ∝λ
Therefore,
1
σ∝
T
• Conductivity is independent of concentration
ne2 λ
σ= implies that σ ∝ n. But bivalent elements like Zn has less conduc-
mvF  
λ
tivity compared to monovalent element. This is because for copper is
  vF
λ
greater than for Zn. As n increases rate of scattering increases hence
vF
practically σ is independent of n.

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• Large value of mean free path

The resistivity of metal is given by
m
ρ=
ne2 τ
The resistivity of copper at 20◦ is 1.69 × 10−8 Ωm and density of free electrons
n = 8.5 × 1028 /m3 . Thus,
m
τ=
ne2 ρ

9.1 × 10−31
τ= = 2.47 × 10−14 s
8.5 × 1028 × (1.6 × 10−19 )2 × 1.69 × 10−8

But
λF
τ=
vF

1 2
mv = EF
2 F

2 × 7.01 × 1.6 × 10−19

vF2 =
9.1 × 10−31

vF = 1.55 × 106 m/s

λF = τ × vF = 2.4 × 20−14 × 1.55 × 106 = 37.8 nm

This value agrees with the experimental value.

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Problems
1. At what temperature we can expect a 10% probability that electrons in silver
have an energy EF = 5.5 eV which is 1% above fermi level.

2. Find the temperature at which there is 1% probability that a state with an

energy 0.5 eV above fermi energy is occupied.

3. Calculate the fermi velocity and the mean free path for the conduction electrons
in silver, given that its fermi energy is 5.5 eV and the relaxation time for
electrons is 3.83 × 10−14 s.

4. Calculate the probability of an electron occupying an energy level 0.02 eV above

the fermi level at 200 K a nd 400 K in a material.

5. Calculate the probability of an electron occupying energy level 0.02 eV above

the fermi level and 0.02 eV below fermi level at 200 K.

6. The fermi level in silver is 5.5 eV. What are the energies for which the probabili-
ties of occupancy at 300 K are 0.99, 0.01 and 0.5. Given 1 joule = 6.24×1018 eV.

7. Compute the fermi energy of zirconium(Zr), which has two valence electrons
per atom. Atomic weight of zinc is 91.22 and its density is 6.51 × 103 kg/m3

8. Calculate the Fermi energy of Cesium metal at zero kelvin which h as one
valence electron per atom. It is a bcc crystal with a lattice constant 6.04 Å.
Given there are two atoms per unit cell for bcc crystal.

9. Aluminium is an fcc crystal with lattice constant 4.05 Å, and the metals has
3 free electrons per atom. Calculate the fermi energy in electron volt for the
metal. Also evaluate its fermi factor at an ambient temperature 300 K for an
energy value 0.1 eV higher than then EF . Given 1 joule = 6.24 × 1018 eV.

10. Show that sum of the probability of occupancy of an energy state at ∆E below
fermi level and that at ∆E above fermi level is unity.

11. Show that occupation probability at E = EF + ∆E is equal to non-occupation

probability at E = EF − ∆E.

12. Calculate the drift velocity and thermal energy of electrons in a metal of thick-
ness 1 mm across which a potential of 1 V is applied at temperature 300 K.
Given the mobility of electron is 40 cm2 /Vs.

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Applied Physics for EEE Stream BPHYEE102

13. Find the relaxation time of conduction electrons in a metal of resistivity 1.54 ×
10−8 Ω − m, if the metal has 5.8 × 1028 conduction electrons per cubic meter.
14. Silver has 5.8 × 1028 conduction electrons per cubic meter. Find the drift
velocity of the conduction electrons if a current of 60 mA flows through a silver
wire of cross sectional area 0.2 mm2 , and also find the current density in it. If
the applied electric field is 0.00476 V/m, evaluate the electrical conductivity of
silver.
15. Consider the silver in metallic state, with one free conduction electron per
atom. Calculate its fermi energy, the density of silver is 10.5 gcm3 and its
atomic weight is 108. [Ans: 5.5 eV]
16. Calculate fermi energy of zinc from data given below: Density of zinc =
7.13 g/cm3 , atomic weight = 65.4, effective mass of a free electron in zinc crystal
= 7.7 × 10−31 kg, Avogadro’s number = 6.02 × 1023 atoms /g. [Ans:11.14 eV]
17. The number of free electrons per cubic meter of sodium is 2.5 × 1028 . Calculate
the value of fermi energy and fermi velocity. [Ans: EF = 3.1 eV, vF = 1.047 ×
106 m/s
18. The relaxation time of conduction electron in copper is 3 × 10−14 s. Find
the thermal conductivity of copper at 0◦ C. Assume density of electron to be
8 × 1028 /m3 . [Ans: 205.675 W/mK]
19. The density of silver is 104 kg/m3 . The atomic weight of silver is 107.9 a.m.u.
Assuming that each silver atom provides one conduction electron, calculate
the density of electrons. The conductivity of silver at 20◦ C is 7 × 107 /Ωm.
Calculate the mobility of electrons in silver and collision time.[Ans: µ = 7.841×
10−5 m2 /Vs, τ = 44.6 ns]
20. If copper desnity d = 8.92 × 10−8 kg/m3 , resistivity of copper, ρ = 1.73 ×
10−8 Ωm, atomic weight M =63.5. Calculate the mobility and the average time
of collision of the electrons in copper, obeying classical laws. [Ans: Mobility =
0.427 × 10−2 m/Vs, τ = 2.43 × 10−14 s]
21. Calculate the number of energy states in an energy interval of 0.02 eV above
fermi energy for sodium crystal of unit volume. Given EF = 3.22 eV. [Ans:
2.46 × 1026 /m3 ]
22. Find the number of energy states per unit volume for a metal at 2.5 eV from
the base. [Ans: 1.788 × 1028 ]

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BPHYEE102 Applied Physics for EEE Stream

23. A certain conductor has electron concentration 5.9 × 1028 /m3 .
What current
1
density in the conductor corresponds to a drift velocity of 1.6 mm/s. Cal-
culate the mobility of charge carriers, given conductivity is 6.22 × 107 mho/m.
[Ans: J = 5.9 × 106 A/m, µ = 6.588 × 10−3 m2 /Vs]

Questions
1. Discuss failures of classical free electron theory.

2. Mention the postulates of Qunatum free electron theory.

3. Define fermi energy, fermi factor and fermi velocity.

4. Define density of energy states.

5. Show that the occupation probability at E = EF + ∆E is equal to the non-

occupation probability at E = EF − ∆E.

6. Discuss the probability of occupation of energy levels by electrons at temper-

ature T = 0 K and T > 0 K, using fermi factor.

7. Explain density of states. Derive an expression for number of allowed energy

states per unit volume of a solid.

8. Describe how quantum free electron theory has been successful in overcoming
the failures of classical free electron theory.

9. Explain the temperature dependence of fermi factor and its effect with occu-
pancy of energy levels.

10. Explain fermi energy and fermi factor. Discuss the probability of occupation
of various energy states by electrons at T = 0K and T > 0K on the basis of
fermi factor.

11. Explain merits of quantum free electron theory.

12. Define drift velocity, mobility, mean time collision and mean free path.

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