SPB9425 Lecture notes 7-10

4.3 Density of states

-The density of states (DOS) is essentially the number of different states at a particular energy
level that electrons are allowed to occupy, i.e. the number of electronic states per unit volume per
unit energy.
-It’s defined as the number of electronic states present in a unit energy range

The density of state 𝐷(∈) is mathematically given by the expression

Ef

 D( E)dE  N
0

3
V  2mE F  2
Where in previous lecture we had N   
3 2   
2

Thus the above equation becomes

3
EF
V  2mE F  2
0 D ( E ) dE   
3 2   2 

Then by expressing the integral in an indefinite form

3 3
V  2mE  2
V  2m  2 1 2
 D( E )dE  3 2  2 
  
 2
2
 2  E dE
 
3
V  2m  2 1 2
D( E )    E , which is the expression for density of state.
2 2   2 

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SPB9425 Lecture notes 7-10

Free electron theory/model

The free electron model is a simple model for the behavior of valence electrons in a crystal
structure of a metallic solid. It was developed principally by Arnold sommerfield who
combined the classical Drude model with quantum mechanical Fermi-Dirac statistics and
hence it also known as the Drude-Sommerfeld model. The free electron Empty lattice
Approximation forms the basis of the band structure model known as nearly free electron
mode. Given its simplicity, it is surprisingly successful in explaining many experimental
phenomena, especially

 The Wiedmann-Franz law which relates electrical conductivity and thermal

conductivity
 The emperature dependence of the heat capacity
 The shape of electronic density of states
 The range of binding energy values
 Electrical conductivities
 Thermal electron emission and field electron emission from bulk metals

As in Drude model, valence electrons are assumed to be completely detached from their ions
(forming an electron gas). As an ideal gas, electron-electron interactions are completely
neglected. The electrostatic fields in metals are weak because of the screening effect.

The crystal lattice is not explicitly taken into account. A quantum mechanical justification is
given by Bloch’s Theorem; an unbound electron moves in a periodic potential as a free electron
in vacuum, except for the electron mass m becoming an effective mass 𝑚∗ which may deviate
considerably from m ( one can even use negative effective mass to describe conduction by
electron holes). Effective masses can be derived from band structure computations. While the
static lattice does not hinder the motion of electrons, electrons can be scattered by impurities and
by phonons; these two interactions determine electrical and thermal conductivity
(superconductivity requires a more refined theory than the free electron model).

According to Pauli Exclusion Principle, each phase space element (∆𝑘)3(∆𝑥)3 can be occupied
only by two electrons (one per quantum number). This restriction of available electron states is
taken into account by Fermi-Dirac statistics. Main predictions of the free-electron model are
derived by the sommerfield expansion of the Fermi-Dirac occupancy for energies around the
Fermi-level.

Application of free electron theory/model in determination of electrical conductivity of

materials

Based on the classical free electron theory of solids, we can derive the relation for the
ne2
conductivity of a metal in the form   .
m
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SPB9425 Lecture notes 7-10

-Let us consider a simple form of the Lorentz force law in which we take the magnetic field
induction 𝐵̅ = 0 and the electric field intensity E
̅ = constant.
The electron dynamics in this case is
𝑑𝑣⃗ 1
𝑚 ( + 𝑣⃗) = −𝑒𝐸⃗⃗ … … … … … … … … . . (𝑎)
𝑑𝑡 𝜏
In steady state conditions the electron velocity is a constant and is referred to a drift velocity (𝑣⃗).
⃗⃗
𝑑𝑣
Thus = 0 ; since 𝑣⃗ = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑑𝑡
Then (i) becomes
𝑚𝑣⃗
= −𝑒𝐸⃗⃗ … … … … … … … … … (𝑏)
𝜏
𝜏𝑒𝐸
𝑉 = (− ) … … … … … … … (𝑐)
𝑚
The electrical current density 𝐽⃗ of the electron is given by
qE ne 2E
J  nqv, but v  , J
m m
Ohm’s law can also be expressed as
ne 2
J  E Therefore  
m

5.0 Distribution laws

 Maxwell –Boltzmann statistics

 Bose-Einstein Statistics
 Fermi- Dirac Statistics

The statistical distribution laws can be used to describe many of the observed properties of
different kinds of physical systems having different properties. There are four kinds of systems
which together provide a description of the many diverse phenomena in physics.

a) Identical but distinguishable particles

b) Identical indistinguishable particles
c) Identical, indistinguishable particles of half-integral spins
d) Identical, indistinguishable particles of integral spin.

Now, assume that we have as assembly of N particles and with a total energy E. We assume that
the assembly is in statistical equilibrium at this total energy E. The problem now is to find out in
how many different ways (p), all of which is equally probable, these N particles can be arranged

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SPB9425 Lecture notes 7-10

and distributed among the various stationary energy states of the assembly and to find out what is
statistically the most probable such distribution.

Total number of particles is the sum of total of particles assigned to each energy state
∞

𝑁 = 𝑛1 + 𝑛2 + ⋯ 𝑛𝑘 = ∑ 𝑛𝑘
𝑘=1
While the total energy
∞

𝐸 = 𝑛1 ∈1 + 𝑛2 ∈2 + ⋯ 𝑛𝑘 ∈𝑘 = ∑ 𝑛𝑘 ∈𝑘
𝑘=1

5.1 Maxwell-Boltzmann distribution

a) For identical and distinguishable particles

We can 1st have arrangement is N ways, 2nd is (N-1), 3rd is (N-2) etc. to N! ways
Since the particles are identical, the sequence of arrangement is irrelevant, can start at
∈1 , ∈2 ….∈𝑘 . The total number of ways in which energy levels can be filled up with N
systems is given by
𝑁!
𝑃=
𝑛1 ! 𝑛2 ! … , 𝑛𝑘 !
For the whole assembly the probability is given by the product over K of all such
expressions as given by
1
𝑃 = 𝑁! ∏
𝑛𝑘 !
𝑘
-Consider the degeneracy in a state ∈𝑘 as 𝑤𝑘 . It implies that; there is no restriction as to
how particles permute. The 1st does not affect the 2nd, 3rd,….. 𝑛𝑘 𝑡ℎ .

Hence the total number of ways in which 𝒏𝒌 systems can be assigned to 𝒘𝒌 states of the 𝒌𝒕𝒉
levels is (𝑤𝑘 )𝑛𝑘 .

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SPB9425 Lecture notes 7-10

-Since this replicates in other states, the total number of ways in which N systems can be
assigned to stationary energy levels of the assembly is

𝑁!
(𝑤 )𝑛𝑘 (𝑤2 )𝑛𝑘 … (𝑤𝑘 )𝑛𝑘
𝑛1 ! 𝑛2 ! … , 𝑛𝑘 ! 1

This is the Maxwell-Boltzmann distribution count.

(𝑤𝑘 )𝑛𝑘
𝐶𝑀−𝐵 = 𝑁! ∏
𝑛𝑘 !
𝑘

b) For identical indistinguishable particles

Since the systems are indistinguishable, their permutation is 1(must be excluded). The rest of the
permutation remains as a above leading to the classical distribution

𝑁! (𝑤𝑘 )𝑛𝑘 (𝑤𝑘 )𝑛𝑘

𝐶𝐶𝑙𝑎𝑠𝑠𝑖𝑐𝑎𝑙 = ∏ =∏
𝑁! 𝑛𝑘 ! 𝑛𝑘 !
𝑘 𝑘

c) For identical indistinguishable systems with integral spins

Here one of the level is 𝒘𝒌 fixed (partitioned).

While the remaining (𝒘𝒌 − 𝟏) 𝑎𝑟𝑒 𝑡ℎ𝑒𝑛 𝑝𝑒𝑟𝑚𝑢𝑡𝑒𝑑. This can be permuted in (𝒏𝒌 + 𝒘𝒌 − 𝟏)!
ways. The 𝒏𝒌 (𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠) and the number of partitions (𝒘𝒌 − 𝟏) are a like, such permutations
must be excluded, hence;

(𝒏𝒌 + 𝒘𝒌 − 𝟏)!
𝑷=
𝒏𝒌 ! (𝒘𝒌 − 𝟏)!

-For the whole assembly the probability is given by the product over k of all such expressions as
given by the Bose-Einstein distribution

(𝒏𝒌 + 𝒘𝒌 − 𝟏)!
𝑪𝑩−𝑬 = ∏
𝒏𝒌 ! (𝒘𝒌 − 𝟏)!
𝑘

d) For identical indistinguishable systems with half-integral spins

Constraint is made by the fact that such particles obey the Pauli Exclusion Principle.,
hence no more than one particle can occupy an energy state. Thus once the 1st energy has
been filled, the 2nd will fill, followed by the next one in that order. Since there are 𝒘𝒌
states in the 𝒌𝒕𝒉 level, the 1st is filled in 𝒘𝒌 ways, the second in (𝒘𝒌 − 𝟏), next in
(𝒘𝒌 − 𝟐) etc. The permutations in the ∈𝒌 states is in the 𝒘𝒌 ! Ways.

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SPB9425 Lecture notes 7-10

 For Pauli exclusion principle to be fully obeyed then 𝒘𝒌 ≫ 𝒏𝒌 .

 The unfilled states (𝒘𝒌 −𝒏𝒌 ) are identical and must be excluded, similarly, the
permutations of 𝒏𝒌 identical particles must be excluded.
 For the whole assembly the probability is given by the product over K of all
expressions as given by the Fermi-Dirac distribution:

𝒘𝒌 !
𝑪𝑭−𝑫 = ∏
𝒏𝒌 ! (𝒘𝒌 − 𝒏𝒌 )!
𝑘

5.2 Bose-Einstein statistics

Bose-Einstein statistics (B-E statistics) is one of two possible ways in which a collection of
indistinguishable particles may occupy a set of available discrete energy states. The aggregation
of particles in the same state, which is a characteristic of particles obeying the B-E statistics,
accounts for the cohesive streaming of laser light and the frictionless creeping of superfluid
helium. The theory of this behavior was developed (1924-25) by Albert Einstein and Satyendra
Nath Bose, who recognized that a collection of identical and indistinguishable particles can be
distributed in this way.

The Bose-Einstein statistics apply only to those particles not limited to single occupancy of the
same state that is particles that do not obey the Pauli Exclusion Principle restrictions. Such
particles have integer values of spin and are named bosons, after the statistics that correctly
described their behavior.

Concept

At low temperatures, bosons behave differently from fermions (which obey the Fermi-Dirac
statistics) in that an unlimited number of them can “condense” into the same energy state. This
apparently unusual property also gives rise to the special state of matter-Bose Einstein
Condensate. Fermi-Dirac and Bose-Einstein statistics apply when quantum effect is important
and the particles are “indistinguishable”. Quantum effects appear if the concentration of particles
𝑁
satisfies 𝑉 ≥ 𝑛𝑞

Where N is the number of particles, V is the volume and 𝑛𝑞 is quantum concentration, for which
the inter-particle distance is equal to the thermal de Broglie wavelength, so that the wave-
functions of the particles are touching but not overlapping. Fermi-Dirac statistics apply to
fermions (particle that obey the Pauli Exclusion Principle), and the Bose-Einstein apply to
bosons. As the quantum concentration depends on temperature, most systems at high
temperature obey the classical Dirac and Bose-Einstein become Maxwell-Boltzmann statistics at
high temperature or at low concentration.

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SPB9425 Lecture notes 7-10

B-E statistics was introduced for photons in 1924 by Bose and generalized to atoms by Einstein
in 1924-25. The expected number of particles in an energy state i for B-E statistics is
𝒈𝒊
𝒏𝒊 = (𝝐𝒊 −𝝁)⁄
𝒆 𝑲𝑻 −𝟏

With 𝝐𝒊 > 𝝁 and where 𝒏𝒊 is the number of particles in state i, 𝒈𝒊 is the degeneracy of state i, 𝝐𝒊
is the energy of the ith state , 𝝁 is the chemical potential, K is the Boltzmann constant, and T is
the absolute temperature. For comparison, the average number of fermions with energy 𝝐𝒊 given
by Fermi-Dirac statistics has the form
𝒈𝒊
̃(𝝐
𝒏𝒊 𝒊 ) = (𝝐𝒊 −𝝁)⁄
𝒆 𝑲𝑻 +𝟏

B-E statistics reduces to the Rayleigh-Jeans law distribution for 𝐾𝑇 ≫ 𝜖𝑖 − 𝜇, thus

𝑔𝑖 𝐾𝑇
𝑛𝑖 =
𝜖𝑖 − 𝜇

Derivation of the Bose-Einstein distribution

Suppose we have a number of energy levels, labeled by index i, each level having energy 𝜖𝑖 and
containing a total number of 𝑛𝑖 particles. Suppose each level contains 𝑔𝑖 distinct sublevels, all of
which have the same energy, and which are distinguishable. For example, two particles may
have different momenta, in which case they are distinguishable from each other, yet they can
still have the energy. The value of 𝑔𝑖 associated with level i is called the “degeneracy” of that
energy level. Any number of bosons can occupy the same sublevel.

Let 𝜔(𝑛, 𝑔) be the number of ways of distributing 𝑛 particles among the 𝑔 sublevels of an
energy level. There is only one way of distributing 𝑛 particles with one sublevel 𝜔(𝑛, 1) = 1.
Thus it easy t see that there are ((𝑛 + 1) ways of distributing 𝑛 particles in two sublevels which
we will write as:

(𝑛 + 1)!
𝜔(𝑛, 2) =
𝑛! 1!
Then it can be seen that the number of ways of distributing 𝑛 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 in three sublevels is

𝜔(𝑛, 𝑔)𝜔(𝑛, 2) + 𝜔(𝑛 − 1,2) + ⋯ + 𝜔(1,2) + 𝜔(0,2)

So that

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SPB9425 Lecture notes 7-10

𝑛 𝑛
(𝑛 − 𝑘 + 1)! (𝑛 + 2)!
𝜔(𝑛, 𝑔) = ∑ 𝜔(𝑛 − 𝑘, 2) = ∑ =
(𝑛 − 𝑘)! 1! 𝑛! 2!
𝑘=0 𝑘=0

Where we have used the following theorem involving binomial coefficients:

𝑛
(𝑘 + 𝑎)! (𝑛 + 𝑎 + 1)!
∑ =
𝑘! 𝑎! 𝑛! (𝑎 + 1)!
𝑘=0

And continuing this process, we can see that 𝜔(𝑛, 𝑔) is just a binomial coefficient.

(𝑛 + 𝑔 − 1)!
𝜔(𝑛, 𝑔) =
𝑛! (𝑔 − 1)!

For example the population number for two particles in three sublevels are; 200, 110, 101, 020,
011, or 002 which is for a total of six which equals 4!/(2!2!). The number of ways that a set of
occupation numbers 𝑛𝑖 can be realized is the product of the ways that each individual energy
level can be populated.

(𝑛𝑖 + 𝑔𝑖 + 1)! (𝑛𝑖 + 𝑔𝑖 )!

𝑊 = ∏ 𝜔(𝑛𝑖 , 𝑔𝑖 ) = ∏ ≈∏
𝑛𝑖 (𝑔𝑖 − 1)! 𝑛𝑖 (𝑔𝑖 − 1)!
𝑖 𝑖 𝑖

Where the approximation assumes that 𝑛𝑖 ≫ 1

Now, following the same procedure used in deriving the Maxwell-Boltzmann statistics, we wish
to find the set of 𝑛𝑖 which 𝑊 is maximized, subject to the constraint that there be a fixed total
number of particles, and a fixed total energy. The maxima of 𝑊 and ln(𝑊) occur at the same
value of 𝑛𝑖 and since it is easier to accomplish mathematically, we will maximize the later
function instead. We constrain our solution using Lagrange multipliers forming the function

𝑓(𝑛𝑖 ) = ∑(𝑛𝑖 + 𝑔𝑖 )ln(𝑛𝑖 + 𝑔𝑖 ) − 𝑛𝑖 ln(𝑛𝑖 ) + 𝛼 (𝑁 − ∑ 𝑛𝑖 ) + 𝛽 (𝐸 − ∑ 𝑛𝑖 ∈𝑖 ) + 𝐾.

𝑖

Where K is the sum of a number of terms which are not functions of the 𝑛𝑖 . Now taking the
derivatives with respect to 𝑛𝑖 , and setting the results to zero and solving for 𝑛𝑖 , yields the Bose-
Einstein population numbers;
𝑔𝑖
𝑛𝑖 = 𝛼+𝛽𝜖
𝑒 𝑖 −1
By a process similar to that outlined in the Maxwell-Boltzmann statistics section, it can be seen
that 𝑑𝑙𝑛𝑊 = 𝛼𝑑𝑁 + 𝛽𝑑𝐸 which, on using Boltzmann’s relationship 𝑆 = 𝑘𝑙𝑛𝑊, becomes a
1
statement of the second law of thermodynamics at constant volume, and it follows that 𝛽 = 𝐾𝑇

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SPB9425 Lecture notes 7-10

𝜇
and 𝛼 = − 𝐾𝑇 , where S is the entropy, 𝜇 is the chemical potential, K Boltzmann’s constant and T
is the temperature, so that finally;
𝑔𝑖
𝑛𝑖 = (𝜖𝑖 −𝜇)⁄
𝑒 𝐾𝑇 −1
Above formula is sometimes usually written as
𝑔𝑖 𝜇
𝑛𝑖 = 𝜖𝑖
⁄𝐾𝑇
, where 𝑍 = exp(𝐾𝑇) is the absolute activity.
𝑒 ⁄
𝑧−1

5.3 Fermi-Dirac statistics

Fermi-Dirac statistics is a part of the science of physics that describes the energies of single
particles in a system comprising many identical particles that obey the Pauli exclusion principle.
It was named after Enrico Fermi and Paul Dirac, who each discovered it independently, although
Enrico Fermi defined the statistics earlier than Paul Dirac.

Fermi-Dirac (F-D) statistics applies to identical particles with half-odd-integer spin in a system
in thermal equilibrium. Additionally, the particles in this system are assumed to be have
negligible mutual interaction. This allows the many-particle system to be described in terms of
single-particle energy states. The result is the F-D distribution of particles over these states and
includes the condition that no two particles can occupy the same state, which has a considerable
effect on the properties of the system. Since F-D statistics applies to particles with half-integer
spin, these particles have come to be called fermions. It is commonly applied to electrons, which
are fermions with spin 1⁄2 . Fermi-Dirac statistics is a part of the more general field of statistical
mechanics and uses the principles of quantum mechanics.

Before the introduction of Fermi-Dirac statistics in1926, understanding some aspect of electron
behavior was difficult due to seemingly contradictory phenomena. For example, the electronic
heat capacity of a metal at room temperature seemed to come from 100 times fewer electrons
than were in the electric current. It was also difficult to understand why the emission currents,
generated by applying high electric fields to metals at room temperature, were almost
independent of temperature. The difficulty encountered by the electronic theory of metals at that
time was due to considering that electrons were (according to classical statistics theory) all
equivalent. In other words it was believed that each electron contributed to the specific heat an
amount on the order of the Boltzmann constant k. This statistical problem remained unsolved
until the discovery of F-D statistics in 1926.

F-D statistics was applied by Fowler (in 1926) to describe the collapse of a star of white dwarf.
In 1927, Sommerfeld applied it to electrons in metals. Thus Fermi-Dirac statistics continues to
be an important part of physics following the F-D distribution

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SPB9425 Lecture notes 7-10

Now, for a system of identical fermions, the average number of fermions in a single-particle
state given by the Fermi-Dirac (F-D) distribution
𝑔𝑖
𝑛̅𝑖 = (𝜖𝑖 −𝜇)⁄
𝑒 𝐾𝑇 +1
Where K is K Boltzmann’s constant and T is the absolute temperature, ∈𝑖 is the energy of the
single-particle state i, and 𝜇 is the chemical potential. At T = 0 K, the chemical potential is
equal to the Fermi energy. For the case of electron in a semiconductor, 𝜇 is also called the
Fermi-level.

The F-D distribution is only valid if the number of fermions in the system is large enough so that
adding one more fermions to the system has negligible effect to 𝜇. Since the F-D distribution
was derived using the Pauli exclusion-principle, which allows at most one electron to occupy
each possible state, a result is that 0 < 𝑛̅𝑖 < 1

The average number of fermions with energy ∈𝑖 can be found by multiplying the F-D
distribution 𝑛𝑖 by the degeneracy 𝑔𝑖 (the number of states with energy ∈𝑖
𝑔𝑖
𝑛̅(∈𝑖 ) = 𝑔𝑖 𝑛̅𝑖 = (𝜖𝑖 −𝜇)⁄
𝑒 𝐾𝑇 +1
When 𝑔𝑖 ≥ 2, it is possible than 𝑛̅(∈𝑖 ) > 1 since there is more than one state that can be
occupied by fermions with the same energy ∈𝑖

Now, when a quasi-quantum of energies ∈ has associated density of state 𝑔(∈) i.e the number of
states per unit energy range, per unit volume) the average number of fermions per unit energy
range per unit volume is 𝑁̅ (∈) = 𝑔(∈)𝐹(∈); where F(∈𝑖 ) is called the Fermi function and is the
same function that is used for the f-D distribution 𝑛𝑖
𝑔𝑖 𝑔𝑖 (∈)
𝐹(∈) = (∈−𝜇)⁄
̅ (∈) =
; thus 𝑁 (∈−𝜇)⁄
𝑒 𝐾𝑇 +1 𝑒 𝐾𝑇 +1

Assignment 2

1. Distinguish between M-B, B-E and F-D statistics

𝜀 −𝜇 −1
𝑛𝑖 ( 𝑖 )
2. Show that the Bose-Einstein distribution function is given by 𝑔 = (𝑒 𝑘𝐵 𝑇 − 1) where
𝑖

the symbols have their usual meanings

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SPB9425 Lecture notes 7-10

MAGNETIC PROPERTIES
 Ferromagnetism
 Paramagnetism
 Diamagnetism

11