OLIVIER Statistical Physics - Distribution Functions - OS - 2020

Statistical Physics:
Distribution functions of particles

Maxwell-Boltzmann statistics
Fermi-Dirac statistics
Bose-Einstein statistics
NanoPhot 2020-2021
Olivier Simonetti
1
2
Table of contents
Chapter 1 Introduction to distribution functions................................................................................. 5
Chapter 2 Maxwell-Boltzmann distribution ......................................................................................... 9
2.1 Introduction............................................................................................................................. 9
2.2 Derivation of the Maxwell-Boltzmann statistics ................................................................... 11
2.2.1 Number of ways to accomplish the entire system ........................................................ 11
2.2.1 Problem position ........................................................................................................... 12
2.2.1 Lagrange method of undetermined multipliers ............................................................ 12
Chapter 3 Fermi-Dirac distribution .................................................................................................... 15
3.1 Introduction........................................................................................................................... 15
3.2 Derivation of the Fermi-Dirac statistics ................................................................................. 15
Chapter 4 Bose-Einstein distribution ................................................................................................. 19
4.1 Introduction........................................................................................................................... 19
4.2 Derivation of the Bose-Einstein statistics .............................................................................. 19
Chapter 5 Signification of the Lagrange multipliers ........................................................................... 23
5.1 Signification of .................................................................................................................... 23
5.1.1 Total number of particles .............................................................................................. 23
5.1.2 Total energy ................................................................................................................... 23
5.2 Signification of .................................................................................................................... 25
5.3 The three distribution functions ........................................................................................... 27
Chapter 6 Annexes ............................................................................................................................. 29
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4
Chapter 1 Introduction to distribution functions
To explain the physical characteristics of a system we must understand the behaviour of the particles
inside.
Particles in a system occupy states and levels. Each level has a particular energy. Each level can be
constituted by sublevels which can be constituted by several states. The number of sublevels is the
degeneracy of the level. Degenerate states are different states that have the same energy level.
Obviously a particle occupying a level has the energy of this level.
Particles can be describe as classical or as quantum particles. (The term “particles” is general here and
can sometime be molecules.)
Classical particles obey to the classical physics (Newtonian mechanics, thermodynamic…) which is
determinist (same cause implies the same consequence). Classical particles are distinguishable (we
can follow a given particle among all the others). In theory, you can attributed a position and a velocity
at each classical particle in the system. Molecules are classical “particles”.
Quantum particles obey to the quantum physics (quantum mechanics) which is non-determinist (an
intrinsic uncertainty exist). In theory, you cannot attributed an exact position and an exact value of the
velocity at each quantum particle in the system. Quantum particles obey at a certain uncertainty
principle: the Heisenberg uncertainty principle. Electrons, photons, phonons… are quantum particles.
Quantum particles are indistinguishable.
The accessible states are determined by all the interactions that undergo the particles. Quantum
mechanics show that when the particles are confined in space (within the atom or within a “box”) the
accessible states are quantized. Each level can host a given number of particles. The number of
quantum particles which can be put in a state depend on the type of particles.
Quantum particles can be fermions (electrons, protons…) or bosons (photons, phonons, Higgs
bosons…).
Fermions obey to the Pauli exclusion principle.
The Pauli exclusion principle not allow that two identical fermions occupy the same state. Identical
particles in quantum mechanics mean particles with exactly the same quantum numbers; especially
particles with the same energy and the same spin. In consequence, the number of accessible states in
a given level is limited. In other words, the number of particles occupying a level is limited. The
presence of accessible and forbidden energy in matter is a direct consequence of the Pauli exclusion
principle.
In contrary, bosons do not obey to the Pauli exclusion principle. In consequence, the number of
accessible states in a given level is unlimited. In other words, the number of particles occupying a level
is unlimited.
In the systems we will deal with (solids and gases) the number of particles is hugged. Therefore, only
statistics can be used to describe the macroscopic behaviour of the system (even in the classical case).
The theory which deals with this kind of systems is the statistical mechanics. The statistical mechanics
describe the macrostate (i.e. measurable, observable) of the system from the microstate. A microstate
corresponds to a particular distribution of particles in the accessible states. Distribution functions are
nothing but the probability density functions used to describe the probability with which a particular
particle can occupy a particular state. The probability that a particular energy state is occupied is
described by statistics depending on the type of particles.
5
Maxwell Boltzmann statistics deals with classical particles (as molecules) which are considered
distinguishable
Fermi-Dirac statistics deals with Fermions which are considered indistinguishable and obey to Pauli
exclusion principle.
Bose-Einstein statistics deals with bosons (photons, phonons, Higgs bosons…) which are considered
indistinguishable and do not obey to Pauli exclusion principle.
The Maxwell Boltzmann statistics are classical statistics. The Fermi-Dirac and the Bose-Einstein
statistics are quantum statistics.
In each case and independently of the type of the particles, the system constituted of particles,
is associated with the following parameters:
The energy levels, i.e. accessible states: , , ,…,
The number of states at each energy levels (degeneracy): , , ,…,
The number of electrons occupying each energy levels: , , ,…,
The level of energy of degeneracy is occupied by particles.
We call a particular distribution of particles which occupy each state. For a given the number of
particles occupying each state is frozen.
In each case, the total number of electrons in the system and the total energy of the system are
constant. We assume the conservation of the total number of particles and the conservation of the
total energy. Then:
1-1
And:
1-2
The type of particles determines the manner how all the particles within the system are distributed in
each level. Schematically, each level of energy of degeneracy can be represented by a ring. (Fig.
1-1).
6
Fig. 1-1: Each level of energy of degeneracy can be represented by a ring. The particles are
represented by the black points. Here 6 particles in the energy level of degeneracy 8.
The question is: How are distributed the 6 particles in the 8 states of the level?
The macrostate is represented by a particular distribution of the particles in each energy level
. The distribution which describe the macrostate is noted .
They are many ways to put particles in the energy level of degeneracy . The number of ways to
have a particular distribution , , is determined by the usual permutation and combination
formula and probabilities. The type of the particles (classical, fermions or bosons) will give constraints
on how to put those particles in the available states. The number will be depend on the type
of particles.
A probability is associated to each particular distribution .
The statistical physics assumes that i) the macrostate at the equilibrium and represented by the
distribution is the distribution for which the number of ways to have , , is maximum and
ii) that the distribution is the most probable distribution and the probability, , is much more
probable than anyone else distribution; i.e. ≫ .
The idea that the macrostate represented by corresponds to the maximum is used to explain
why the second law of thermodynamics comes about when a system is composed of a very large
number of small components. The second law of thermodynamics states that the total entropy of an
isolated system can only increase over time. Isolated systems spontaneously evolve towards
thermodynamic equilibrium, the state with maximum entropy. The value of the entropy represents
the rate of disorder of the system.
It was Boltzmann (in 1870) who identified ≡ as a measure of the entropy of the system. A
gas not in equilibrium will evolve to maximise its entropy just because this represents the maximum
probability among the possible states of its constituents. The entropy is then defined as:
! ln 1-3
The Eq. 1-3 is inscribed on the Boltzmann gravestone (ln ≡ log is the natural logarithm).
Fig. 1-2: Boltzmann’ tombstone, with his entropy formula in Vienna (Austria).
In practice, for one kind of particles, what we are going to do will be:
1. determine ,
2. maximize (in fact ln ) in regard of the two constraints given by Eq. 1-1 and 1-2,
7
3. and using the assumptions given above, the statistics, & , we are looking for will be simply
'
given by ) (.
(
To find & , we have to look at the number of ways in which you can accomplish anyone
given and then maximums it.
We first derive the classical Maxwell Boltzmann statistics and, after, we derive the quantum Fermi-
Dirac and the Bose-Einstein statistics.
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Chapter 2 Maxwell-Boltzmann distribution
2.1 Introduction
In classical physics, the evolution of any systems is determinist. Which means that a same cause implies
the same consequence. In theory, if you know the initial condition of a classical system a classical
theory can determine is evolution. However, in practice, if you deal with system with a huge number
of elements, there exists a degree of “uncertainty” with respect to the fact that the motion of every
single particle at all times cannot be determined in practice in any large system. Only one mole of gas
contains 6x1023 molecules!
James Clerk Maxwell developed his kinetic theory of gases in 1859. He determined the distribution of
velocities among the molecules of gas. Later in 1871 Ludwig Boltzmann generalized the Maxwell’s
kinetic theory of gases to express the distribution of energies among the molecules.
Maxwell described the gas as billions of molecules moving rapidly and randomly, colliding with each
other and the walls of the container (Fig. 2-1). His description was qualitatively consistent with the
physical properties of gases: increase the temperature causes an increase of the velocity of the
molecules and an increase of the frequency of collision with the other molecules and the walls.
Fig. 2-1: A container of volume * with a huge number of molecules inside.
Maxwell made four assumptions:

• The diameter of the molecules is much smaller than the distance between them.
• The collisions between molecules are elastic (conservation of the energy).
• The molecules move between collisions without interacting as a constant speed in a straight
line.
• The positions and velocities of the molecules are initially at random.
The total number of particles is fixed. The Maxwell-Boltzmann distribution of the velocity of molecules
in an ideal gas is depicted in Fig. 2-2.
9
Fig. 2-2: Molecules speed Maxwell’s distribution at different temperature.
Fig. 2-3: Molecules speed Maxwell’s distribution at a given temperature.
The temperature and the volume of the system are constant. Maxwell’s theory was based on statistical
averages to see if the macrostates, (i.e. measurable, observable) could be predicted from the
microstates.
The thermal equilibrium is established when the temperatures of the subsystems are equal. So what
is the nature of the equilibrium distribution for a system of N non-interacting gas particles?
Statistical mechanics are based on the idea that the equilibrium state of a thermodynamic medium is
the macroscopic state that corresponds with the most probable microscopic state.
Note that the Maxwell-Boltzmann statistics is the statistics which is considered in the Drude model to
determine the distribution of the electron velocities in the system.
• Electrons are identical and distinguishable.
• We consider a large collection of electrons.
• In a system the total number of electrons is constant (conservation of the number of
particles)
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• At the thermal equilibrium the total energy is also constant (conservation of the total
energy).
This assumption fails to explain some features of metals.
2.2 Derivation of the Maxwell-Boltzmann statistics

The Maxwell-Boltzmann statistics describes the distribution of particles across energy levels, for a
system in thermal equilibrium. The Maxwell-Boltzmann statistics deals with classical particles.
2.2.1 Number of ways to accomplish the entire system
Consider the simplest case, a system of non-interacting classical particles. A classical system is
defined as:
• There are no restrictions on how many particles can be put into any state simultaneously.
• The particles are distinguishable, i.e. each particle is labelled for all time.
The system we must to deal with and the associated parameters are given by:
The energy levels available for the system, i.e. accessible states (fixed): , , ,…,
The number of particles occupying each energy levels (not fixed): , , ,…,
The number of ways in which you can create a particular distribution ,+ , is given by:
! !
+
! ! -! … ! ∏ !
2-1
The Eq. 2-1 represents the number of ways to have a specific microstate. In other words, it corresponds
to how many ways can you arrange particles such that are of one kind, are of one kind, -
are of one kind, are of another kind. See Annex 2 for details.
Physically, each accessible state (i.e. each containers) corresponds to a state in which each particle can
be put. The states are classified in terms of their energy and degeneracy . Degenerate states are
different states that have the same energy level. The number of states available at a given level is
called the degeneracy of that level.
In the classical case, there are no restrictions on how many particles that can be put into any one state.
The system we must to deal with and the associated parameters are then given by:
The energy levels, i.e. accessible states (fixed): , , ,…,
The number of states at each energy levels (fixed): , , ,…,
The number of electrons occupying each energy levels (not fixed): , , ,…,
'(
The possible arrangements of particles into sublevels is: .
Therefore, if the system has a particular state that has a particular degeneracy, there is an additional
of '( for that particular state. See Annex 2 for details.
Therefore, the total number of ways in which you can create a particular distribution , , for a
collection of classical particles is given by:
!
0 12 '(
∏ ! 2-2
11
Fig. 2-4: Example of a particular distribution in a level of energy of degeneracy 8. The 6
particles are represented by the black points and labelled with a number (particles are
distinguishable).
What to know is the combination of , , ,…, , , which maximizes the value of .

2.2.1 Problem position
We must find the distribution which maximize . We had previously called the distribution
which maximize . But to find the maximum we have to take into account the two
constraints we have to consider in this system. The two constraints are i) conservation of the number
of particles (Eq. 2-5) and ii) the conservation of the total energy (Eq. 2-6).
Conservation of the number of particles: the total number of electrons is constant. Then:
34567 57 2-3
Conservation of the total energy: the total energy is constant. Then:
34567 57 2-4
To solve the problem we have to maximize W given by the Eq. 2-2 subject of the two constraints
given by the Eq. 2-3 and the Eq. 2-4. To solve this problem, we use a mathematical method called the
Lagrange method of undetermined multipliers.
2.2.1 Lagrange method of undetermined multipliers
Rather than to maximize we will maximize ln . ln is given by:
ln ln !9 ln : ln ! 2-5
According the Stirling’s approximation (true if X > 20): ln ;! ; ln ; : ; . The Eq. 2-5 becomes:
ln ln : 9 ln : < ln : = 2-6
12
In order to maximize ln we must find the values of > ? corresponding to the distribution .
The maximum will be reached for δln 0 according to B . In Eq. 2-6 is fixed and only
the values of > ? can change. Then:
1
B ln 0:09 B ln : 0B ln 9 B :B 1 0 2-7
And:
B ln : <B ln = 0 2-8
Then:
ln : ln B 0 2-9
Then:
ln B 0 2-10
The first constraint corresponding to the conservation of the number of particles (Eq. 2-3) leads to:
B 0 2-11
And the second constraint corresponding to the conservation of the total energy (Eq. 2-4) leads to:
B 0 2-12
To maximize ln W subject of the two constraints we have to consider the system of three
equations 2-10, 2-11 and 2-12. To solve this problem, we use the mathematical method refer to
2.2.1.1 Lagrange method
The Lagrange method of undetermined multipliers assumed that it exists two constants and such
as:
< D. 2-8= < D. 2-11= : < D. 2-12 = 2-13
This imply that:
0ln : 9 1B 0 2-14
'
The Eq. 3-6 is always true regardless to B . This imply the term Hln ) ( : 9 I is always equal to
(
zero. Then:
13
ln : 9 0 2-15
And:
J KLM( 2-16
Using the assumption that the equilibrium state of a thermodynamic medium is the macroscopic state
that corresponds with the most probable microscopic state. The more probable macroscale
distribution W is then much more probable than all the others distributions N and the value of
W is much larger than the value of the sum of all the others distributions. As shown in the Annex
2 this assumption leads to:
& ≈ for 2-17
Consequently, the Boltzmann distribution is given by:
& J KLM(
2-18
We must give the meaning of the Lagrange multipliers and . This will be done in 0.
The Maxwell-Boltzmann distribution shows that the number of particles decreases exponentially when
the energy level of states increases (Fig. 2-5).
Fig. 2-5: The Maxwell-Boltzmann statistics.
Note that, the Maxwell-Boltzmann statistics well describe ideal gas particles but, as it is explained in
the course of solid-state physics, MB distribution is not well applicable for electrons in a solid.
14
Chapter 3 Fermi-Dirac distribution
3.1 Introduction
In particle physics, a fermion is a quantum particle that follows Fermi-Dirac statistics and generally has
half odd integer spin 1/2, 3/2 etc. These particles obey the Pauli exclusion principle and are
indistinguishable.
Some fermions are elementary particles, such as the electrons.
This part describes the Fermi-Dirac statistics.
3.2 Derivation of the Fermi-Dirac statistics

The Fermi-Dirac (FD) statistics describes the distribution of fermions across energy levels, for a system
in thermal equilibrium.
So, we must find the number of ways to accomplish the entire system.
We have to put particles in states. As the particles are fermions and that fermions obey to the
Pauli exclusion principle, we can put only 0 or 1 particles by state (Pauli exclusion principle). So, in the
energy level , there is occupied states and : empty states (Fig. 3-1). The number of ways
+ to put the particles in the states of the energy level .is simply the number of possible
permutations between full states and : empty states.
The number of permutations between states is !, but the permutations of the full states between
them, !, and of the empty states between them, : !, do not change the microstate of .
Therefore, the number of ways + to put particles in states at an energy level is given by:
!
+
! : !
3-1
For a given energy level ,+ represents the number of ways to jumbling fermions up in
states.
is the number of ways + to accomplish , , time to the number of ways + to
accomplish , , time to the number of ways + to accomplish , , - and so on.
Therefore:
2+ 3-2
And:
15
!
2
! : !
3-3
Note that is a function of the R variables corresponding to the R values of the > ?
corresponding to the particular distribution .

fermions are represented by the black points. Due to the Pauli exclusion principle only 0 or 1 fermion
can occupy a state.
of particles (Eq. 3-4) and ii) the conservation of the total energy (3-5).
34567 57 3-4
34567 57 3-5
To solve the problem we have to maximize given by the Eq. 3-3 subject of the two constraints
given by the Eq. 3-4 and the Eq. 3-5. To solve this problem, we use a mathematical method called the
To simplify the problem, rather than to directly maximize we will maximize ln . ln
is given by:
ln <ln ! : ln ! : ln : != 3-6
16
ln < ln : ln : : ln : = 3-7
The maximum will be reached for δln 0 according to B . In Eq. 3-7 the set of > ? are fixed
and the set of > ? are the variables. Then:
1
δln 00 : B ln : B
1
3-8
: :B ln : : : :B 1 0
:
Finally, we have:
:
δln 0B ln S T1 0 3-9
B 0 3-10
B 0 3-11
To maximize ln subject of the two constraints we have to consider the system of three
equations 3-9, 3-10 and 3-11. To solve this problem, we use the Lagrange method of undetermined
multipliers.
as:
< D. 3-9= < D. 3-10= 9 < D. 3-11 = 3-12
This imply that:
:
0: ln S T9 9 1B 0 3-13
)( K'(
The Eq. 3-13 is always true regardless to B . This imply the term H: ln W
'(
X9 9 I is always
equal to zero. Then:
:
: ln S T9 9 0 3-14
And after calculation we obtain:
17
1
J YLM( 91
3-15
distribution is then much more probable than all the others distributions N and the value
of is much larger than the value of the sum of all the others distributions. As shown in the
Annex 2 this assumption leads to:
& ≈ for 3-16
The Eq. 3-17 is the FD statistics when the distribution has been attained:
1
&
J YLM( 91
3-17
Fig. 3-2: Fermi-Dirac statistics with temperature.
18
Chapter 4 Bose-Einstein distribution
4.1 Introduction
In quantum mechanics, a boson is a particle that follows Bose–Einstein statistics and generally has
integer spin 0, 1, 2 etc.
Especially, photons and phonons are bosons.
This part describes the Bose-Einstein statistics.
4.2 Derivation of the Bose-Einstein statistics

The Bose-Einstein (BE) statistics describes the distribution of fermions across energy levels, for a
system in thermal equilibrium.
So, we must find the number of ways to accomplish the entire system.
In a level , we have to put particles in states. As the particles are bosons, we can put any number
of bosons by states (Fig. 4-1). In the ring of the Fig. 4-1 we just have to permute particles and the
separation items. The total number of these 9 items is 9 !. But, all the permutation
between particles, !, do not give a new distribution because the particles are indistinguishable. The
same for the separation items: all the permutation between separation items, !, do not give a new
distribution.
The number of ways + to put the bosons in the states of the level .is given by:
9 !
+
! !
4-1
The total number of ways on all the energy level is given by the product of the + :
9 !
2+ 2
! !
4-2
Note that is a function of the R variables corresponding to the R values of the > ?
corresponding to the particular distribution .
19
bosons are represented by the black points. Any number of bosons can be put by states.
of particles (Eq. 4-3) and ii) the conservation of the total energy (Eq. 4-4).
34567 57 4-3
34567 57 4-4
To solve the problem we have to maximize given by the Eq. 3-3 subject of the two constraints
given. To solve this problem, we use a mathematical method called the Lagrange method of
undetermined multipliers.
To simplify the problem, rather than to directly maximize we will maximize ln . ln
is given by:
ln <ln 9 ! : ln ! : ln != 4-5
ln < 9 ln 9 : ln : ln = 4-6
The maximum will be reached for δln 0 according to B . In Eq. 4-6 the set of > ? are fixed
and the set of > ? are the variables.
After calculation we obtain:
20
9
δln 0B ln S T1 0 4-7
B 0 4-8
B 0 4-9
To maximize ln subject of the two constraints we have to consider the system of three
equations 4-7, 4-8 and4-9. To solve this problem, we use the Lagrange method of undetermined
multipliers.
as:
< D. 4-7= < D. 4-8= 9 < D. 4-9 = 4-10
This imply that:
9
0: ln S T9 9 1B 0 4-11
)( Y'(
The Eq. 4-11 is always true regardless to B . This imply the term H: ln W '(
X9 9 I is always
equal to zero. Then:
9
: ln S T9 9 0 4-12
And after calculation we obtain:
1
J YLM( :1
4-13
distribution is then much more probable than all the others distributions N and the value
of is much larger than the value of the sum of all the others distributions. As shown in the
Annex 2 this assumption leads to:
& ≈ for 4-14
The Eq. 4-15 is the FD statistics when the distribution has been attained:
21
1
&
J YLM( 91
4-15
22
Chapter 5 Signification of the Lagrange multipliers
To truly understand the signification of the Lagrange multipliers and one must have prior
knowledge of statistical thermodynamics.
The Eq. 2-13, 3-12 and 4-10 show that the parameter is related to the conservation of the total
number of particles and the parameter is related to the conservation of the total energy. Those
parameters are then independent of the nature of the particles. (This why we will take some results
from the derivative of the MB statistics for and from the derivative of the FD statistics for .)
5.1 Signification of
To find , we must determine the total number of particles and the total energy of the
system.
5.1.1 Total number of particles
If the states can be assumed as a quasi-continuum (states are closely spaced in energy), the total
number of particles is given by:
Y`
\ & ]^ _ 5-1
Where ]^ is the density of states given by (this expression is calculated elsewhere in the course
of solid-state physics):
-
* 2b
]^ S T . / 5-2
2a ħ
Introducing Eq. 2-18 and Eq. 5-2 in Eq. 5-1 we obtain:
- Y`
* 2b
S T J \ /
J KLM _
2a ħ
5-3
Using the standard integral:
Y`
Γ 591
\ e f J K g _e fY
5-4
Where Γ is the Gamma function (https://mathworld.wolfram.com/GammaFunction.html). Eq. 5-3

becomes:
- 3
* 2b Γ W2X
S T J
5-5
2a ħ -/
5.1.2 Total energy

The total energy, , of the system can be obtained by:
23
Y`
\ & ]^ _ 5-6
Introducing Eq. 2-18 and Eq. 5-2 in 5-6 we obtain:
- Y`
* 2b
S T J \ -/
J KLM _
2a ħ
5-7
Using the standard integral again (Eq. 5-4):
- 5
* 2b ΓW X
S T J 2 5-8
2a ħ j/
By using the results obtain in an ideal gas (see Annex in the course of solid-state physics) we can write:
3
!k
2
5-9
Where ! 1.380649 ×  10K -

JK-1 is the Boltzmann constant.
M
From Eq. 5-5, 5-8 and 5-9 the ratio 'nonpq is rewritten:
nonpq
- 5
* 2b Γ W2X
W X J 3
2a ħ j/
3 !k
2
5-10
-
* 2b Γ W2X
W X J
2a ħ -/
And:
5
1 Γ W2X 3
3 !k
2
5-11
Γ W2X
Using the relation (https://mathworld.wolfram.com/GammaFunction.html):
Γ 195 5Γ 5 5-12
We have:
5 3 3 3
ΓS T Γ S1 9 T ΓS T
2 2 2 2
5-13
Using Eq. 5-13 in Eq. 5-11, we obtain:
3 3
1 2 Γ W2X 3
3 !k
2
5-14
Γ W2X
24
Therefore, we have the relation for :
1
!k
5-15
5.2 Signification of
We have called the number of ways to have a particular distribution in R levels of the system
and we have calculated the most probable distribution by maximizing ln . From the statistical
ln we define a thermodynamic parameter which is the entropy of the system. The entropy is
given by:
! ln 5-16
As we have already seen, the equilibrium of the system corresponds to the maximum of and then,
correspond to the maximum of entropy . is the number of microstates consistent with the given
macrostate. In other word a system reaching an equilibrium reaches the maximum of disorder. In
thermodynamic, the entropy represents the rate of disorder of a system.
The Eq. 5-16 show that has the dimension of ! (JK-1), therefore k has the dimension of an energy.
k is the disorder energy of the system.
The difference between the total energy and the disorder energy k of the system is the free
energy r:
r :k 5-17
From Eq. 1-2 and Eq. 1-3 the free energy r is given by:
r : ! k ln s ln + t 5-18
If we assume that there is a variation of the number of particles in the system of _ , there is also
a variation _ of the parameter and a variation _r of the free energy r. We have:
_ _
_ _ 5-19
And:
_r _ _ ln +
: !k
_ _ _
5-20
_r _ ln + _
u : !k v
_ _ _
5-21
)( !
From Eq. 3-1, +
'( ! )( K'( !
, we have:
25
!
ln + ln S T <ln ! : ln ! : ln : !=
! : !
5-22
According the Stirling’s approximation: ln ;! ; ln ; : ; . The Eq. 5-22 becomes:
ln + < ln : ln : : ln : = 5-23
And then:
_ ln + :
ln S T
_
5-24
Moreover, from the expression of the Fermi-Dirac statistics given by Eq. 3-15 we can write:
:
J YLM(
5-25
And:
_ ln + :
ln S T 9
_
5-26
Putting Eq. 5-26 in Eq. 5-21 we obtain:
_r _
: !k 9
_ _ 5-27
wx y
From Eq. 5-15, , the Eq. 5-27 gives:
_r _ _
: !k : !k
_ _ _ 5-28
The parameter is then given by:
1 _r
:
k_
5-29
z{
The quantity z' represents the variation of the free energy of the system in function of the number
nonpq
of particles. This quantity is called the chemical potential of the system and it is noted |.
|
!k
5-30
In a system of fermions (electrons for example) the chemical potential is often called the energy Fermi
level and it is noted { .
{
!k
5-31
26
Remark: we have given the signification of the Lagrange multiplier for a system of fermions but the
results will be the same with a system of bosons.
Remark: do not confuse the Fermi level defined as the electron highest occupied energy in a solid at 0
K and the chemical potential. At temperature > 0 K and for the metal the two values are slightly
different. In semiconductors the values are very different.
5.3 The three distribution functions

Here is the three statistics for each kind of particles: classical; fermions and bosons.
The Maxwell-Boltzmann distribution is then given by:
1
&}!
J MKM~ ⁄wx y
5-32
The Fermi-Dirac distribution is then given by:
1
&{€
J MKM~ ⁄wx y 91
5-33
The Bose-Einstein distribution is then given by:
1
&!M
J MKM~ ⁄wx y :1
5-34
Fig. 5-1: Comparison between the three statistics.
27
28
Chapter 6 Annexes
Annex 1: Statistical physics approximation
Definitions
The systems we must to deal with are volume in which particles are able to move. The system can be
a gas or a solid.
In those systems the number of particles is hugged. Therefore, only statistics can be used to describe
the macroscopic behaviour of the system. The theory which deals with this kind of systems is the
statistical physics. The statistical physics describe the macrostate (i.e. measurable, observable) of the
system from the microstate. A microstate corresponds to a particular distribution of particles in the
accessible states. Distribution functions are nothing but the probability density functions used to
describe the probability with which a particular particle can occupy a particular state. The probability
that a particular energy state is occupied is described by statistics depending on the type of particles.
Particles in a system occupy accessible states. A level can be constituted of several states. Each level
has a particular energy . Obviously, a particle occupying a level has the energy of this level. Each level
can be constituted by sublevels which can be constituted by several states.
The system we must to deal with and the associated parameters are then given by:
The energy levels, (fixed): , , ,…,
The number of states at each energy levels, i.e. accessible states (fixed): , , ,…,
We call a particular distribution of particles which occupy each state. For a given the number of
particles occupying each state is frozen.
• & is the probability that a level at an energy is occupied.
• & • is the conditional probability, for a particular , i.e. & • is the probability that
the state at energy is occupied by particles conditionally to a specific distribution .
The conditional probability is given by:
& • 6-1
We now looking for the probability that the system has a specific distribution . is given
by:
6-2
‚ƒ‚„…
Where is the number of ways in which you can create a specific microstate and ‚ƒ‚„…
∑ is the total number of ways that creates all possible specific .
The probability that a state at an energy is occupied is given by:
29
& ‡& • ˆ 6-3
And according to Eq. 6-2the Eq. 6-3 becomes:
∑ ‡& • ˆ
& 6-4
‚ƒ‚„…
The Eq. 6-4 is the most complete picture of the probability that the state of energy level is occupied.
Statistical physics assumption used

The more probable distribution that you can get is obtained for the bigger number of ways to create
the microstate . For , is maximum. is the number of ways in which the most
probable macroscale can be attained.
As already mentioned previously, statistical physics is based on the idea that the equilibrium state of
a thermodynamic medium is the macroscopic state that corresponds with the most probable
microstate. The more probable distribution is then much more probable than all the others
distributions N and the value of is much larger than the value of the sum of all the others
distributions. This approximation is valid when the number of particles is huge. So, the approximation
is valid for the system we are dealing with. In other words, there exist a distribution , which results
in the maximum possible value for the corresponding . This can be expressed by:
≈1 6-5
‚ƒ‚„…
Therefore:
& ≈ & | 6-6
According Eq. 6-1, when the distribution is we have:
& ≈ for 6-7
To find & , we have to look at the number of ways in which you can accomplish anyone
given and then maximums it.
30
Annex 2: Multiplicity function (from lecture of Melanie Hill)
First, what we going to do is to determine the number of microstates within any given configuration,
i.e. the number of ways in which objects can be arranged into R distinct groups, also called the
“multiplicity function”.
The multiplicity function determines the number of ways in which objects can be arranged into
R containers.
31
32
33

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Statistical Physics:

Distribution functions of particles

Fig. 2-1: A container of volume * with a huge number of molecules inside.

Maxwell made four assumptions:

Fig. 2-3: Molecules speed Maxwell’s distribution at a given temperature.

2.2 Derivation of the Maxwell-Boltzmann statistics

What to know is the combination of , , ,…, , , which maximizes the value of .

Conservation of the total energy: the total energy is constant. Then:

< D. 2-8= < D. 2-11= : < D. 2-12 = 2-13

This imply that:

& ≈ for 2-17

Consequently, the Boltzmann distribution is given by:

Fig. 2-5: The Maxwell-Boltzmann statistics.

3.2 Derivation of the Fermi-Dirac statistics

Fig. 3-1: Example of a particular distribution in a level of energy of degeneracy 8. The 6

Conservation of the total energy: the total energy is constant. Then:

< D. 3-9= < D. 3-10= 9 < D. 3-11 = 3-12

This imply that:

And after calculation we obtain:

& ≈ for 3-16

Fig. 3-2: Fermi-Dirac statistics with temperature.

4.2 Derivation of the Bose-Einstein statistics

Conservation of the total energy: the total energy is constant. Then:

< D. 4-7= < D. 4-8= 9 < D. 4-9 = 4-10

This imply that:

And after calculation we obtain:

& ≈ for 4-14

Introducing Eq. 2-18 and Eq. 5-2 in Eq. 5-1 we obtain:

Using the standard integral:

Where Γ is the Gamma function (https://mathworld.wolfram.com/GammaFunction.html). Eq. 5-3

5.1.2 Total energy

Introducing Eq. 2-18 and Eq. 5-2 in 5-6 we obtain:

Using the standard integral again (Eq. 5-4):

Where ! 1.380649 × 10K -

Using the relation (https://mathworld.wolfram.com/GammaFunction.html):

Using Eq. 5-13 in Eq. 5-11, we obtain:

According the Stirling’s approximation: ln ;! ; ln ; : ; . The Eq. 5-22 becomes:

Putting Eq. 5-26 in Eq. 5-21 we obtain:

The parameter is then given by:

5.3 The three distribution functions

The Fermi-Dirac distribution is then given by:

The Bose-Einstein distribution is then given by:

Fig. 5-1: Comparison between the three statistics.

And according to Eq. 6-2the Eq. 6-3 becomes:

Statistical physics assumption used

& ≈ & | 6-6

According Eq. 6-1, when the distribution is we have:

& ≈ for 6-7

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Where ! 1.380649 ×  10K -