B.Tech CSE-DS, B.Tech CSE-AIML, B.

Tech CSE-CYS 2024 and Semester-I

Semiconductor Physics (BBS00015)
Class 2024-25 ODD

Study Material
(Semiconductor Physics, BBS00015)
Module II part 1
Contents
1 Classical theory of free electrons .....................................................................................................................1

1.1 Basic assumptions of Drude model ..................................................................................................................1

1.2 Application of Drude model .............................................................................................................................2

1.2.1 DC electrical conductivity of metal ...............................................................................................................2

1.2.2 Mobility of electrons.....................................................................................................................................3

1.2.3 Temperature dependence of resistivity .......................................................................................................4

1.2.4 Thermal conductivity and Wiedemann-Franz law ........................................................................................4

1.3 Limitations of Drude model ..............................................................................................................................5

1.4 Drawbacks of the classical theory of free electrons .........................................................................................6

2 Quantum theory of free electrons....................................................................................................................6

2.1 Fermi-Dirac statistics ........................................................................................................................................6

2.3 Density of states (D(E)): ..................................................................................................................................7

2.4 Electronic heat capacity....................................................................................................................................9

2.5 Comparision between Classical and Quantum free electron theory .............................................................10

1 Classical theory of free electrons

The classical free electron theory, also known as the Drude model of the free electron, was proposed in 1900 by
German physicist Paul Drude to explain the transport properties of electrons in metals. Drude assumed a simple
picture of electrons and nuclei in a metal. There are two types of electrons, core electrons and valance electrons.
Core electrons together with the nucleus form the ions that are immobile. The loosely bound electrons in the
outermost shells can move freely and thus form a “sea” of free electrons inside the metal (represented by the
horizontal lines in Fig. 1). These free electrons (known as conduction electron) are primarily responsible for different
phenomena, like electrical conduction, thermal conduction, etc., in a metal. Drude built his model based on a few
assumptions which are similar to that of the kinetic theory of gas.

1.1 Basic assumptions of Drude model

• Electrons move along a straight line between collisions (in the absence of any electromagnetic field).
Electrons do not apply any force on other electrons and the effect of electron-ion interaction is also ignored.

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• The probability of collision per unit time is 1/τ, where τ is the mean free time between two successive
collisions. The probability of any collision during an infinitesimal time interval dt is dt/τ and it is independent
of the position or velocity of the electron.

Fig. 1: Schematic diagram of electrons in a metal of atomic number 𝑍𝑎 . Z outermost electrons are weakly bound to
the nucleus and are primarily responsible for electrical and thermal conduction. 𝑍𝑎 − Z core electrons are
tightly bound to the nucleus. The core electrons and the nucleus together form the ion cores in a metal that,
unlike the conduction electrons, remain fixed at their position.

• After a collision, electrons move in a random direction with a speed appropriate to the temperature of the
region where the collision happened. In other words, the hotter the region; the higher the speed of the
emerging electrons after the collision.

1.2 Application of Drude model

1.2.1 DC electrical conductivity of metal

Before going into the details let’s understand a few terms.

• n = number density, i.e., number of particles per unit volume.

• τ = average time between two successive collisions, also known as mean free time.

• λ = average distance between two successive collisions known as mean free path.

• 𝑣⃗𝑑 = drift velocity is the average velocity with which the free electrons get drifted towards the positive end of
the conductor under the influence of an external electric field.

• 𝑗⃗ = current density, i.e., number of charge carriers flowing per unit time per unit area normal to the direction
of flow of charge.

Let’s consider n charged particles per unit volume with drift velocity 𝑣⃗𝑑 pass through an area A, normal to the
direction of the drift velocity, in time dt. If q is the charge per particle, the total amount of charge flowing in time
dt is qn(vddtA), where vddtA is the volume of the cylinder formed in time dt. Hence current flowing per unit time
per unit area is qnvd. Since in a metal, freely moving charge carriers are the electrons, i.e., q = −e, the magnitude of
current density is given by

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j = −nevd (1)

Since in absence of any external electric field electrons are randomly moving, the average magnitude of drift
velocity is zero, i.e., < vd >= 0. Hence the current density is zero which is correct since without any external
electromagnetic field current in metal is always zero.

Let’s consider v0 is the velocity of an electron just after a collision and at this moment an external electric field 𝐸⃗⃗
is switched on. In the presence of the electric field force on an electron is (−𝑒𝐸⃗⃗ ) and hence the acceleration of an
electron is (−e𝐸⃗⃗ )/m. After time t if 𝑣⃗ is the velocity of the electron then

𝑒𝐸⃗⃗
𝑣⃗ = 𝑣⃗0 − 𝑡
𝑚

𝑒𝐸⃗⃗
Or, < 𝑣⃗ >=< 𝑣⃗0 > − <𝑡> (2)
𝑚

𝑒𝐸⃗⃗
Or, < 𝑣⃗ > = τ (by definition τ = ⟨t⟩).
𝑚

Since 𝑣⃗ 0 is a random velocity, its average magnitude is zero. Also, the average value of time is mean-free time.
Therefore Eq. 2 shows the expression of the drift velocity of an electron in the presence of an external electric field.
Substituting the value of drift velocity in Eq. 1 we get,
𝑛𝑒 2 τ
𝑗⃗ = 𝐸⃗⃗
𝑚

Considering the alternative form of Ohm’s law, i.e., 𝑗⃗⃗= σ𝐸⃗⃗ , we can write the expression for electrical conductivity
as
ne 2τ
σ=
m . (3)

Substituting the values of τ,n, and other constants one can find that the calculated value of electrical conductivity
of different metals agrees well up to a fair accuracy with the experimentally measured values of σ.

1.2.2 Mobility of electrons

Mobility measures how quickly a charge carrier (electron in general) can move through metal when an external
electric field is applied. In a steady state, the drift velocity per unit electric field is the estimate of mobility µ.

drift velocity
𝜇 = 𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑓𝑖𝑒𝑙𝑑
𝑒𝐸τ
𝑚 𝑒τ
= = (4)
𝐸 𝑚

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1.2.3 Temperature dependence of resistivity

In the absence of any external electric field, under the steady-state condition, the average speed 𝑣̅ of an electron
in a metal can be determined using the concepts of the kinetic theory of gasses.
1 3
𝑚𝑣̅ 2 = 𝑘𝐵 𝑇
2 2
3𝑘𝐵 𝑇
⇒ 𝑣̅ = √
𝑚
The mean free time is τ = λ/𝑣̅ , where λ is the mean free path. Eq. 3 can be expressed as follows,
𝑛𝑒 2 𝜏
𝜎=
𝑚

𝑛𝑒 2 𝜆 𝑛𝑒 2 𝜆 𝑛𝑒 2 𝜆
= = =
𝑚𝑣⃗ 3𝑘 𝑇 √3𝑚𝑘𝐵 𝑇
𝑚√ 𝑚𝐵

√3𝑚𝑘𝐵 𝑇
So, 𝜌=
𝑛𝑒 2 𝜆

where ρ is resistivity. According to the assumptions of Drude’s model, the mean free path (λ) of an electron is
independent of temperature. Therefore the resistivity is proportional to the square root of the temperature
(𝜌 ∝ √𝑇). The experimental measurement, however, shows that the resistivity of metal is proportional to the
temperature, i.e., ρ ∝ T. Therefore it is clear that the classical free electron model fails to determine the correct
temperature dependence of the resistivity of a metal.

1.2.4 Thermal conductivity and Wiedemann-Franz law

Thermal conductivity expresses how efficiently heat energy can propagate through a material via the conduction
method. Quantitatively, thermal conductivity is the rate at which heat energy flows by conduction through a unit
area, normal to the direction of the temperature gradient, of a material. A more formal definition of thermal
conductivity (κ) following Fourier’s law is
𝜕 𝜕 𝜕
⃗⃗𝑇 = −𝜅 [𝑖̂ + 𝑗̂
𝑗⃗𝑞 = −𝜅∇ + 𝑘̂ ] 𝑇
𝜕𝑥 𝜕𝑦 𝜕𝑧
𝑑𝑇
𝑗𝑞 = −𝜅 𝑑𝑥 (in one dimension)
(5)

where jq is the thermal current density, i.e., heat energy flowing per unit time per unit area, normal to the direction
𝑑𝑇
of flow of heat. 𝑑𝑥
is the temperature gradient or the change in temperature per unit length in space. Since heat
energy flows from high-temperature to low-temperature regions, the directions of temperature gradient and heat
flow are mutually opposite. For this reason, there is a minus in the Eq. 5.
Without going into the details of the derivation (not required for this course!), we start with the expression of the
thermal conductivity of a metal derived from the Drude model.
1
𝜅 = 3 𝑣𝑑2 𝜏𝐶𝑉 (6)

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where Cv is the heat capacity, or, the heat required to raise the temperature of the unit mass of a given substance.
Drude assumed, similar to the kinetic theory of gas, at room temperature (or, at a temperature range between
approximately 0◦C and 100◦C) the average drift velocity of the electrons in a metal can be estimated from the
1 3
relation 2 𝑚𝑣𝑑2 = 2 𝑘𝐵 𝑇. This relation, however, is not a valid assumption in the case of electrons in a metal. The
actual value of the mean-square speed of electrons in a metal at room temperature is at least an order of
magnitude higher. Hence Drude underestimated the mean-square speed of electrons in a metal at room
temperature. Also, Drude assumed, like the gas molecules, the heat capacity of a metal at room temperature can
be written as, CV = (3/2)nkB. This assumption is also far from reality. In fact, there is almost no electronic
contribution to the heat capacity of metal at room temperature. At room temperature, the heat capacity of metal
is primarily due to the lattice vibration. Therefore in Drude’s calculation, the value of CV is overestimated by at
least 100 times.
Nevertheless, substituting the values of vd and CV in Eq. 6 and considering the expression of electrical conductivity
from Eq. 3 we can write;
3 3
𝜅 1 (𝑚 𝑘𝐵 𝑇) 𝜏(2 𝑛𝑘𝐵 )
=
𝜎 3 𝑛𝑒 2 𝜏
𝑚

𝜅 3 𝑘𝐵 2
= ( ) 𝑇 (7)
𝜎 2 𝑒
Wiedemann-Franz law This is an empirical law proposed by Gustav Widemann and Rudolph Franz in 1853. It
states that the ratio of thermal conductivity to the electrical conductivity of a metal is directly proportional to its
temperature with a proportionality constant, which is, to a fair accuracy, the same for all metals. The
proportionality constant is called Lorentz Number, after the name of Ludvig Lorentz, who estimated the value of
the constant is 1872. In other words, k/σ = LT, where L is the Lorentz number.

The experimentally measured value of L at high temperature (say, 0−100◦C) for different metals is approximately
2.2 × 10−8 watt−ohm/K2.
In his original calculation, despite making two invalid assumptions, i.e., the underestimated value of vd and
𝜅
overestimated value of CV, Drude, luckily, estimated the ratio of 𝜎𝑇 to be 2.22 × 10−8 watt−ohm/K2. Even though
this value is surprisingly close to the experimentally measured value, it is clear that Drude model or classical theory
of free electrons cannot accurately estimate the thermal conductivity of a metal.

1.3 Limitations of Drude model

The classical theory of free electrons fails to explain the following:

• Thermal conductivity

• Thermo-electricity

• Hall effect

• Magnetoresistance

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1.4 Drawbacks of the classical theory of free electrons

The following conditions are not satisfied in Drude’s model.

1. electrons cannot be treated classically – these are Fermions.

2. electrons are indistinguishable particles.

3. electrons obey Pauli’s exclusion principle.

2 Quantum theory of free electrons

Clearly, classical theory is inadequate in explaining the dynamics of electrons in a metal. Therefore, we need an
improved theory. As a next step, we have Quantum free electron theory, which is a microscopic theory developed
by Arnold Sommerfeld in 1928. Sommerfeld model or the quantum free electron theory retains almost all aspects
of Drude’s model with the following modifications.

• It treats electrons as indistinguishable particles – Fermions.

• It considers electronic energies are discrete – treats the electron as a particle in a box.

• It uses Fermi-Dirac statistics to fill up the energy states with electrons.

• It obeys the Pauli exclusion principle to distribute the electrons in the available energy states.

Before going into further details, let’s briefly understand the following topics.

(a) Fermion: These are indistinguishable particles with half-integer spin obeying the Pauli exclusion principle.
Examples: electrons, protons, neutrons, etc. A single electron can have either +1/2 (up) or -1/2 (down) spin.

(b) Pauli exclusion principle: It says that no two electrons (fermions, broadly speaking) can have the same set of
quantum numbers. In simpler words, two electrons of the same spin cannot occupy the same energy level;
they must have opposite spins.

(c) Fermi-Dirac Distribution: Fermi-Dirac distribution is a statistical rule introduced by Enrico Fermi and Paul
Dirac to distribute fermions (electrons) over available energy states.

2.1 Fermi-Dirac statistics:

Fermi-Dirac distribution tells us the probability that an

energy level is occupied by a fermion (electron in our
case). Mathematically, the probability function is given
as,
1
𝑓(𝐸) = 𝐸−𝐸𝐹
(8)
exp( )+1
𝐾𝐵 𝑇

Fig 2.Fermi-Dirac distribution function plotted as a function of

energy for different temperatures

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where, E is the energy, 𝐸𝐹 is the Fermi energy, Fermi energy and and T is the temperature. f(E) is also called
occupational probability.

2.2 Fermi energy:

Fermi energy or Fermi level is the highest occupied energy level at temperature 𝑇 = 0 K. At the absolute zero
temperature, all the energy states or energy levels, up to the Fermi energy, are completely occupied (two
electrons of opposite spin per energy level) and all energy levels higher than the Fermi energy are unoccupied.
Then at the absolute temperature, i.e., 𝑇 = 0 K, the eq. 8 takes the form,
1 if 𝐸 ≤ 𝐸𝑓
𝑓(𝐸) = {
0 if 𝐸 > 𝐸𝑓
Therefore, unlike the classical theory, Sommerfeld’s quantum theory does not allow all the electrons to have the
same energy, even at temperature 𝑇 = 0 K. The electrons occupy discrete energy levels (two electrons per
energy level) up to the Fermi energy at 𝑇 = 0 K.
For temperatures higher than 0K, the Fermi energy may not be the highest occupied energy level since for some
electrons there is a finite probability that they may occupy the higher energy states. From the Eq. 8, clearly, for
any temperature T > 0, at the Fermi energy, i.e., 𝐸 = 𝐸𝐹 , f(E) = 1/2. Thus, for temperature higher than 0 K, the
Fermi energy (EF) may be defined as the energy level where the probability of occupation is 1/2. Unlike, the
Fermi energy at T = 0 K (let’s denote it as 𝐸𝐹0 ), Fermi energy at any finite temperature is not the highest occupied
level; instead, it lies between the occupied levels and unoccupied levels. Apparently, the position of the Fermi
level is not fixed, but it depends on temperature. An approximate relationship between 𝐸𝐹 and temperature (T) is
given as follows:
2
𝜋 2 𝐾𝐵 𝑇
𝐸𝐹 ≅ 𝐸𝐹𝑜 {1 − ( ) } (9)
12 𝐸𝐹𝑜
However, in case of metals, since the energy-spacing between the levels are too small (∼ 10−19 eV), the highest
occupied energy level may be considered as the Fermi energy for practical purpose.

2.3 Density of states (D(E)):

The density of states (DOS) is the number of available energy states per unit range of energy. In other words, D(E)
dE is the number of energy states available between energy E and E + dE. If n is the number electrons per unit
𝑑𝑛
volume, 𝑑𝐸 represents the DOS.
We shall determine the functional form of the DOS function in reciprocal space or k-space. Sometimes it is also
referred to as the momentum space. Strictly speaking, “k-space” and “momentum space” are not identical. The
wavevector k has the dimension 1/length whereas the momentum has dimensions (mass×length)/time. In
quantum mechanics, these are related as p = ℏk. The terms “k-space” and “momentum space” are used
interchangeably because the relationship between 𝑘⃗⃗ and 𝑝⃗ is simple, universal and well-known.
In a system of N electrons, the occupied energy levels in the ground state may be represented by points inside a
sphere in the three-dimensional (3D) k-space. In 3D k-space (2π)3/V is the volume that contains exactly one energy
state, where V is the volume in real-space that contains N electrons. Therefore, the total number of available energy
states within a sphere of radius k in the reciprocal space is:
4 3
3 𝜋𝑘
(2𝜋)3
𝑉

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Since each energy level can accommodate two electrons (of opposite spin), total number of electrons within the
sphere of radius k in reciprocal space is given by

4 3
𝜋𝑘
𝑁=23 3
(2𝜋)
𝑉
1𝑉 3
= 𝑘
3 𝜋2
𝑁 𝑘3
⇒ =𝑛= (n = number of electrons per unit volume) (10)
𝑉 3𝜋2

In Sommerfeld’s model, electrons can move freely (potential energy is zero) inside a metal. Therefore, total energy
is only kinetic energy. The momentum is related to kinetic energy, or the total energy in this case, as

𝑝2 ℏ2 𝑘 2
𝐸 = 2𝑚 = 2𝑚
(∵ p = ℏk) (11)
𝑑𝑛 𝑑𝑛 𝑑𝑘 𝑘2 1 ℏ2 𝑘 2
Therefore, DOS can be calculated as the following; 𝐷(𝐸) = 𝑑𝐸 = 𝑑𝑘 𝑑𝐸 = 𝜋2 𝑑𝐸 (∵ 𝐸 = 2𝑚
)
𝑑𝐾

𝑘2 𝑚 𝑚
= 2 2
= ( 2 2) 𝑘
𝜋 ℏ 𝑘 𝜋 ℏ
𝑚 2𝑚𝐸 1
= 2 2 ( 2 )2
𝜋 ℏ ℏ
√2𝑚3/2 1/2
= 𝐸 (12)
𝜋 2 ℏ3
Eq. 12 represents the functional form of the DOS of free electrons in 3D. Similarly, in one-dimensional k-space the
occupied energy levels in the ground state may be represented by points along a line. For a system of N electrons,
(2π)/L is the length that contains exactly one energy state in the one-dimensional k-space, where L is the length
in real space that contains exactly N electrons. Therefore, following the same procedure as before we get,
𝑘 𝑘𝐿 𝑁 𝑘
𝑁 = 2 2𝜋 = 𝜋
⇒𝑛= 𝐿
=𝜋
𝐿

Therefore, the DOS in 1D can be calculated as,

𝑑𝑛 𝑑𝑛 𝑑𝑘 1 1
𝐷(𝐸) = 𝑑𝐸 = 𝑑𝑘 𝑑𝐸 = 𝜋 𝑑𝐸
𝑑𝐾

Since we consider free electrons (i.e., electrons have zero potential energy) the total energy is given by Eq. 11.
𝑑𝐸 ℏ2 𝑘
Therefore 𝑑𝑘 = 𝑚
. Hence the DOS (D(E)) in 1D for free electrons becomes
𝑑𝑛 𝑑𝑛 𝑑𝑘
𝐷(𝐸) = =
𝑑𝐸 𝑑𝑘 𝑑𝐸
1 𝑚
=
𝜋 ℏ2 𝑘
𝑚 2𝑚𝐸 1
= 2 ( 2 )−2
𝜋ℏ ℏ

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𝑚 1 −1/2
=√ 𝐸 (13)
2 𝜋ℏ
Following the same procedure, we can also derive the expression of DOS for free electrons in two-dimension (2D).
In 2D k-space, the energy levels are represented by points inside a square of length k. For a system of N electrons,
(2π)2/A is the area that contains one energy state in the 2D k-space, where A is the area in real space containing
exactly N electrons. Hence, we can write,
𝜋𝑘 2 𝑁 𝑘2
𝑁=2 ⇒ 𝑛 = =
(2𝜋)2 𝐴 2𝜋
𝐴
ℏ2 𝑘 2
Since we consider free electrons, the total energy is 2𝑚
. Therefore, the DOS can be derived as,
𝑑𝑛 𝑑𝑛 𝑑𝑘
𝐷(𝐸) = =
𝑑𝑘 𝑑𝑘 𝑑𝐸
𝑘 1 𝑚
= 𝜋 ℏ2𝑘 = 𝜋ℏ2 (14)
𝑚
Therefore, unlike the 1D and 3D, the DOS in 2D is constant. Please note that the expression of D(E) that we have
derived applies only for the case of the free electrons.
As mentioned earlier, D(E)dE represents the available energy states between the energy E and E + dE, and f(E)
presents the probability of occupation. Therefore, the number of electrons between the energy E and E + dE is
N(E)dE = f(E)D(E)dE. Hence total number of electrons (N) can be determined as,
occupied level
N =∫0 𝑓(𝐸)𝐷(𝐸)𝑑𝐸 (15)
2.4 Electronic heat capacity
3
The average kinetic energy of a free electron, as given by the classical theory of free electrons, is𝐸̅ = 2 𝐾𝑇 . If there
3
are N free electrons per unit volume, the total kinetic energy per unit volume, 𝐸 = 𝑁𝐸̅ = 𝑁𝐾𝑇. Hence specific
2
heat CV can be determined as CV = (3/2)NK. This is what we have learned in the classical free electron theory,
where we assume that all the electrons participate equally toward the contribution of thermal conductivity or
specific heat. But quantum mechanics suggests that when energy is supplied, say, the energy of the order kBT, not
all electrons can occupy the higher energy states or empty states. Only those electrons lying close to the highest
occupied state can move to the unoccupied states and thus contribute toward the specific heat. The number of
𝑘 𝑇 𝑇
such electrons which contribute to the specific heat is of the order𝑁 ( 𝐸𝐵 ) 𝑜𝑟 𝑁 (𝑇 ) where TF is called the Fermi
𝐹 𝐹
3 𝑇
temperature and is defined as EF = kBTF. Hence the expression of specific heat gets modified as 𝐶𝑉 ≅ 2 𝑁𝑘𝐵 (𝑇 ).
𝐹
This indicates that CV is proportional to T and approaches to zero as T tends to 0. Using typical value of T and TF as
300 K and 3000 K respectively, we have
3
𝐶𝑉 ≅ (0.01) (2) 𝑁𝑘𝐵 (16)

The calculated value of CV from the eq. 16 agrees well with the experimental value. Therefore, quantum theory of
free electrons can successfully determine the specific heat of a metal, which could not be done using Drude-
Lorentz’s theory. However, we should remember that the ion-electron interaction is ignored in the classical and
quantum theories. However, in a real solid, this interaction is not negligible. This limitation is taken care of in the
next improved version of the theory, known as Band theory of solids will be our next topic of learning.

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2.5 Comparison between classical and quantum free electron theory

The following assumptions apply to both theories:

1. Both theories are primarily based on the kinetic theory of gasses.

2. The valence electrons move freely throughout the solid. In other words, the mutual repulsion between the
electrons, and the force of attraction between the electrons and ions are ignored.

Differences between Classical and Quantum free electron theory:

Classical free electron theory Quantum free electron theory

Free electrons are treated as distinguishable Free electrons are considered as identical quantum
classical particles. particles, fermions.
The energy of free electrons is a continuous The energy values of the free electrons are
function. discontinuous. i.e., the energy levels are discrete.
The distribution of electrons in various energy levels The distribution of electrons in various energy levels
obeys the Maxwell-Boltzmann statistics. obeys the Fermi-Dirac statistics.

Prepared by the faculty members of the Physics department 10

Brainware University, Kolkata