Statistical mechanics

Dr.Abhilash K P
Syllabus
• Phase space, probability, principle of equal A priori probability,
macrostate and microstate, entropy and thermodynamic probability,
fundamental postulates of statistical mechanics, kinds of ensembles,
Maxwell-Boltzmann law - distribution of velocity - quantum statistics
– Fermi-Dirac distribution law, electron gas, Bose-Einstein distribution
law - photon gas - comparison of three statistics.
 Role of statistical mechanics
• If a system containing large number of molecules, ordinary laws of mechanics
is impossible to apply. Here we relay on the laws of statistical mechanics.
• Probability
• The probability of an event may be defined as the ratio of the number of
cases in which the event occurs to the total number of cases;
• Probability of an event=
• Suppose an event can happen ‘a’ ways and will not happen over ‘b’ ways;
• Then the probability of occurrence of the event =
• The probability of failing the event =
• The sum of this two probability will always be 1;
• The probability of a ‘sure’ event is always 1; and that of an impossible event
is always’0’.
Probability: Real life examples
• 1) Throwing a coin:
• Suppose we toss a coin; The probability to come head up is always :
• The probability to come tail up is always :
• 1) Throwing a die: The die is a regular cube with 6 faces. Out of 6
possible faces only one face will come up at a time. Then the probability
of occurrence of each face is:
• The probability of occurrence of face noted with even numbers : =
• The probability of occurrence of face noted with odd numbers : =
• The probability of occurrence of face noted with any number less than 6
:
• The probability of occurrence of face noted with number 7:0
• This is known as zero probability
 Probability and frequency
• Suppose we toss a coin, say N times and we find that Head appears M times.
Then the frequency of occurrence of an event is given by:

• If a coin tossed 50 times in which 10 of them the coin shows head , then
frequency of occurrence of head is given by : = 0.2;
• But from the classical definition of probability: The probability of occurrence
of head(or tail) is ½ or 0.5. But in actual case it is 0.2. Hence the frequency of
the event and probability are different event.
• If the number of trials N increases to
• P=
 Basic rules of probability
∆𝑉 1
2

• Additive law: Two mutually exclusive events 1 and 2

• Consider two small non-overlapping region
• A particle in rules out its probability of occurrence at ; The two events thus are mutually exclusive;
• Suppose in N trials the particle is found m1 times in and m2 times in
• Thus the probabilities of finding the particle in the two regions are: p1= and p2=;
• The number of times that the particle will be found at least one of the two regions in N trials is
(m1+m2). Hence the probability will be: (P() = =+ = p1+p2
• This law can be generalized for n number of mutually exclusive events giving probabilities p1,p2,p3,p4,
…….pn; Then the Sum of the probabilities of the events= P=p1+p2+p3+……….pn=
• This is known as additive law of probability.
• Multiplication rule:
• The probability of joint occurrence of two independent events is equal to the product of the
probabilities of each of these independent events.
• P=p1 where p1 and p2 are individual events. Also p1=m1/N and p2=m2/N
 Principle of equal A Priori probability
• If we throw a coin there is equal probability of occurrence for head or tail.
Similarly if a box is divided in to two equal parts and a stone is thrown from
above. The probability of the stone to reach each compartment is equal.
• This principle of assuming equal probability for events which are equally
likely to occur is known as the principle of equal a priory probability.
• In the above experiment if the compartments are divided in to unequal
size, equal a priory probability will not holds good.
Permutations and combinations
• The word permutation means arrangement and combination means formation of
groups;
• Consider 4 ‘distinguishable’ objects marked a,b,c and d. Taking any two objects at a
time, the possible arrangements are; ab,ba,ac,ca,ad,da,bc,cb,bd,db,cd,dc. (12
arrangements possible) In arranging this objects order of the arrangement is also
taken in to considerations; cd and dc are two different permutations.
• 4 objects can be arranged in 12 ways by taking two objects at a time. i.e. the number
of permutations =12
• If 3 objects are taken at any time then: the total number of permutation will be 24; i.e.
4
P3=24
• In general nPr=
• 4P2== 12; similarly 4P3= = 24
Combinations
• Combinations are meaningful combinations or groups with out considering
its order of placement.
• The combinations of 4 objects ‘a,b.c,d’ taking two at a time
are:ab,ac,ad,bc,bd,cd; 4C2=6
• Similarly combination of 4 objects “a,b,c,d” taking 3 at a time are:
= abc,abd,acd,bcd: only 4 combinations: i.e. 4C3=4
The number of meaningful combination of n distinguishable objects by taking
r at a time is given by,
• nCr= But nPr=
• In this nPn= = = Since =1
• Similarly nCn= = 1
 Macrostate and microstate
• Each compartment wise distribution of a system of particles is known as a
macrostate.
• Consider 4 distinguishable particles to distribute in two exactly similar
compartments in a box. Let ‘a,b,c,d’ be the particles which when thrown at any
time it must fall in any one of the compartments in the box. The particles have
equal a priory probability to fall on either of the compartment in the box and is
equal to ½. The possible ways in which 4 particles distributed in two
compartments
Compartments are
No.ofgiven
Particlesby,
Distribution 1 Distribution 2 Distribution 3 Distribution 4 Distribution 5

1 0 1 2 3 4
2 4 3 2 1 0

• The 5 different distributions are: (0,4),(1,3),(2,2),(3,1),(4,0); i.e; (0,n), (1,n-1),

………..(n-1,1) and (n,0); Therefore the total number of macrostates for n
 Microstates • For the particles which are
Macrostates Possible arrangements Number of microstates within the macrostates
distinguishable, the
(Thermodynamic probability) W number of possible
Compartment 1 Compartment 2
arrangements in each
(0,4) 0 abcd 1 compartment for the
(1,3) a bcd 4
system of 4 particles
(a,b,c,d) in different
b cda
macrostates are;
c dab
• Each distinct arrangement
d abc
within the macrostate are
(2,2) ab cd 6
the microstate of the
ac bd system. Here there are 4
ad bc particles; Total number of
bc ad microstate are : 24; For a
bd ac system of n particles, the
cd ab
number of microstate= 2n
(3,1) bcd a 4 • In thermodynamic point of
cda b
view, total energy E of the
system can be distributed
dab c
among N particles
abc d
constituting it which
(4,0) abcd 0 1 specifies its microstate.
• Thermodynamic probability: The number of microstates corresponding to
any given macrostate is called its thermodynamic probability.
• It is represented by the letter W. The number of microstate corresponding to
a given macrostate is equal to the number of meaningful arrangements or
permutations of various particles in the microstate excluding the
permutations that are meaningless;
• Number of meaningful arrangements: nCr=
• The number of microstates within a macrostate (r,n-r) is equal to W(r,n-r)=
• Applying this to the example of 4 particles (a,b,c,d) for the macrostate (1,3),
r=1,
• n-r=3 and n =4; W(1,3)= =4
• The thermodynamic probability of any system is related to the temperature T
by the relation:
• Thermodynamic Probability of a macrostate is defined as the ratio of the
number of microstates (thermodynamic probability W) to the total
number of possible microstates of the syatem;
• Pmacro=
• = substituting for W: P(r,n-r)=* =
• Constrains on a system:
• A set of conditions or restrictions that must be obeyed by a system are
known as constrains:
• If 4 particles arranged in two compartments, then total number of
particles in compartment 1 (n1) and total number of particles in
compartment 2 (n2) will be equal to 4; This is a constrain imposed to the
system. n1+n2=N;
• Accessible states:
• Accessible states are the states consistent with the given constrains of the
system.
• Accessible macrostates are the macrostates which are allowed under the
given constrains to that macrostates
• Inaccessible macrostates are the macrostates which are not allowed under
the given constrains to that macrostates;
• Static and dynamic systems;
• A system is considered as a static system if the constituent particles of the
system remains at rest in a particular microstate.
• A system is said to be dynamic if the constituent particles of the system can
move so that the system can move from one microstate to another
microstate.
• Most probable state: The most probable state of a system is that macrostate
which has the maximum probability of occurrence.
Degrees of freedom
• The energy expression for a system involving f co-ordinates of position
and f co-ordinates of momentum. If a system contains single
molecule, then it has f degrees of freedom. If there are N number of
molecules in the system, N molecules have Nf co-ordinates for
position and Nf co-ordinates for momentum. Then the system have
Nf degrees of freedom
Position space, Momentum space, Phase space
• Position space
• Consider a system consisting of N particles distributed, in a given volume V. If the system is
static all particles will remain fixed at various points in space. In this case, to specify the
position of any particles in the three dimensional space, the values of the 3 cartizian co-
ordinate x,y and z which are mutually perpendicular to each other is sufficient. If there are N
particles, the values of 3N co-ordinates, gives complete information about the static system.
• The three dimensional space in which the location of a particle is completely given by the
three position co-ordinates, is known as position space. Position space is f dimensional
• Momentum space: If the system is dynamic , its particle moves with different velocities,
which constitute momenta. A complete specification of such system can not specify by
position co-ordinates only, but with three components of momentum with three velocity
component Vx , Vy, Vz; If m is the mass of the particles moving with a velocity V, its
momentum P=mv; Three components of momentum are px=mvx, py=mvy, pz=mvz
• The momentum of the particle in static motion can be completely specified by three
mutually perpendicular momentum components px, py, pz, in three dimensional space
known as momentum space and a small volume element in momentum space can be
represented by dpxdpydpz. Momentum space is f dimensional.
 Phase space
• A combination of position space and momentum space is known as phase space. Thus Phase
space has 6 dimensions for one paricle; i.e. 3 position co-ordinates and 3 momentum co-
ordinates all mutually perpendicular to each other. The position of a dynamic system in phase
space can be represented by 6 co-ordinates: x,y,z, px, py, pz,. The phase space includes the position
and momentum of the particles. The small elemental volume of phase space can be represented
by: (dx.dy.dz)(dpxdpydpz.) phase space is 6 (2f for n paricles) dimensional.
• The mu-space
• The position of a dynamic system in phase space can be represented by 6 co-ordinates: x,y,z, px,
py, pz,. The phase space includes the position and momentum of the particles. Such a 6
dimentional space fo a “single particle” is called molecular space or mu-space or is 2f
dimensional
• The
• It is a 6N dimensional phase space representation in which a single point represents a state of
entire N particle system and referred as the representative point. Gamma space is highly
useful when dealing with different ensembles . The gamma space is a conceptual Eucledean
space having 2fN rectangular axis.
 Fundamental postulates of statistical Mechanics
• The fundamental postulates/assumptions in statistical mechanics are:
• Any gas under consideration may be considered to be composed of large number of
molecules which are constantly in motion and behave like very small elastic spheres.
• All the cells in phase space are of equal size.
• All accessible microstates corresponding to the possible macrostates are equally
probable. This is most important and fundamental postulates of statistical mechanics.
If we consider the distribution of 4 distinguishable particles a,b,c,d in two cells I,j then:
Probability of microstate (a,b,c,d,o)= =
Probability of the microstate ((a,b,c),d)= * =
Probability of the microstate ((a), (b,c,d))= * =
Probability of the microstate ((a,b), (c,d))= * =
Hence the probability of the all assessable states are equal.
Also,P(E) P(E)
• The equilibrium state of a gas corresponds to the macrostate of maximum probability.
• The total number of molecules is constant. This is in accordance with
the principle of conservation of matter. If n1 is the number of
molecules in cell 1, n2 is in cell 2;and n3 in cell 3 etc. If n is the total
number of molecules then
• n1+n2+n3+n4+…………….Ni =
• The total energy of the system is a constant.
• This is in accordance with the conservation of energy of the system. If
E1 is the energy of the n1 particles in cell 1, E2 is the energy of the n2
particles in cell 2,……..the total energy E is given by;E1n1+E2n2+E3n3+
……..Eini=
 Statistical Ensembles
• In statistical mechanics Gibbs introduced the concept of ensembles. Ensembles
represents a collection of systems, identical in composition and macroscopic
conditions, but existing in different states. The ensembles can be geometrically
represented by the distribution representative points in gamma space.
• Ensemble can be defined as a collection of large number of macroscopically
identical but essentially independent systems. Macroscopically identical means the
system satisfies same macroscopic conditions; example Volume, energy, pressure,
temperature, total number of particles etc.
• Different kinds of ensembles:
• According to Gibbs, there are 3 different types of ensembles.
• 1) Microcanonical ensembles,
• 2)The canonical ensembles
• 3) The grand canonical ensemble.
• The classification is based on the manner in which the system is interacting each
other.
 Microcanonical ensemble
• The microcanonical ensembles are the collection of essentially
independent systems, having the same energy E, Volume V, and number of
particles N. If we consider the identical system, individual systems of a
microcanonical ensemble are separated by rigid, impermeable, and well
insulated walls, such that the values of (E,V,N) for the particular system are
not affected by the other systems. Here the total energy density will be
constant inside the system.
E,V,N E,V,N E,V,N

E,V,N E,V,N E,V,N

E,V,N E,V,N E,V,N

Microcanonical ensemble
 Canonical ensemble
• The canonical ensemble is a collection of essentially independent systems,
having the same temperature (T), volume V and number of identical
particles N. This is achieved by bringing all the systems in thermal contact
with a large heat reservoir at constant temperature T or simply bringing all
of the system in thermal contact with each other.
• The individual systems of the canonical ensemble are separated by rigid,
impermeable, but diathermic walls. Diathermic means the conducting walls.
As the separating walls are conducting, heat can be exchanged between
the systems, till they reach a common temperature T.
• In canonical ensemble system can exchange energy but not matter or
particles
• Probability distribution function is not a constant and is equal to ρ(E)=A
Canonical and grand canonical ensembles

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Canonical ensemble Grandcanonical ensemble

 Grand-canonical ensemble
• In many of the chemical processes, the number of particles within the system
changes continuously. Hence the grand canonical ensemble is a collection of
large number of essentially independent system having the same temperature
T, volume V, and chemical potential separated by rigid, permeable and
conducting walls. As the separating walls are conducting and permeable, the
exchange of heat energy and particles between the systems so that all the
systems arrive at common temperature T and chemical potential .
• Probability distribution function is not a constant and is equal to Ae^
• A system that exchange energy but not matter is called a canonical ensemble,
and the ensemble in which both energy and matter exchange between the
system is called grand Caconical ensemble. On the other hand if a system
neither exchange matter nor energy; such system is called microcanonical
system. Microcanonical system represents an isolated system.
Comparison of different ensembles.
Property Microcanonical Canonical Grand canonical
1) Contact with the Isolated system; Energy Systems are with thermal Systems can exchange
environment and number of particles contact with heat both energy and matter.
are constant reservoir. Hence systems
can exchange energy but
not matter.
2)Fluctuations None Fluctuations in energy Fluctuations in energy
and matter/particles.
3)Probability distribution Probablity density ρ(E)=a ρ(E)=A ρ(E)=Ae^
constant within the range
E to E+dE.
Partition function Z= Z= Z=
 Entropy and probability
• All irreversible process occurs with maximum entropy. In all irreversible process there is
a net increase in entropy and an increase in randomness. Spontaneous irreversible
processes occurs from less probable to more probable state, hence in such processes
Entropy increases.
• The probability of the system in equilibrium it is maximum. In thermodynamic point of
view equilibrium state is having maximum entropy. At equilibrium both entropy and
thermodynamic probability have maximum value.
• Boltzmann’s entropy relation:
• According to thermodynamic relation, the function entropy S of a system is related with
temperature T by the relation:

• According to the statistical approach = k (2)

• from (1) and (2); =
• Integrating ; S=k log (w) (3)
• Equation 3 provides the relation between thermodynamic probability W and the
thermodynamic function S
 Boltzmann’s entropy relation
• According to the principle of statistical mechanics, the temperature is related
to the thermodynamic probability (W) by the relation,
• (2)
• From eq. (1) and (2) we have,

• Integrating we get, S=k log (W) (3)

• His is called the Boltzmann’s entropy relation. Here k is Boltzmann’s constant.
Thus the Boltzmann’s entropy relation states that the entropy of a system is
proportional to the logarithm of thermodynamic probability of that system.
• The entropy of the universe always tends to increase, which in turn means
the W always tends to increase, which in turn means simply that the universe
always changes towards statistically more probable state.
 Maxwell-Boltzmann statistical distribution
• Three kinds of particles
• In most of the assemblies consist of 3 kinds of particles;
Identical but distinguishable particles with out any spin; In quantum terms wave
functions of the particle overlap to a negligible extend. The Maxwell Boltzmann
distribution holds good for this particles. Example- molecules in a gas
Identical and indistinguishable particles with Zero/ integral spin; They can not
be distinguished from one another, because their wave function overlaps; Such
particles are called Bosons; Boson’s do not obey Pauli’s exclusion principle. The
Bose-Einstien statistics holds good for such particles; Example: Photons, Helium
atoms at low temperature. The radiations from a black body can be explained
using B-E statistics;
Identical and indistinguishable particles with odd half-integral spin [1/2,3/2,5/2,
…]; Their wave function overlaps; They are called Fermions; Fermions obey
Pauli’s exclusion principle; They can be represented by Fermi-dirac Statistical
distribution laws; Examples: Electrons, Protons, Neutrons
 Maxwell-Boltzmann Energy distribution law
• Consider a system of N distinguishable particles distributed in phase space, in N
number of boxes.
• In this n1 number of particles having energy E1.
• n2 number of particles having energy E2
and ni number of particles having energy Ei
• Now each energy levels Ei, there will be different quantum states represented
by gi. This gi represents the different degenerate states within the energy level
Ei
• Thus n1 number of particles having energy E1 and degeneracy g1
• n2 number of particles having energy E2 and degeneracy g2
and ni number of particles having energy Ei and degeneracy gi.
Here, the total number of particles = n1+n2+n3+………ni = (1)
And total energy E=n1E1+n2E2+n3E3+……………….niEi = = Ei (2)
• The priory probability of distribution in most probable degenerate states are
given by : G = *…………………*
• Also, the thermodynamic probability for N particles in N distinguishable
microstates is given by, (Ω) =
• The total probability (W) = G* Ω (3)
w=* *…………………*
Taking log on both sides;
Log (w)= log - + (4)
Applying Sterling’s approximation: log x!= [xlog x]-x, the eq.4 becomes;
Log (w)= [N log - - -+
Log (w)= [N log + i (5)
The most probable distribution of the particles among the energy states in
equilibrium is that the probability of occurrence is maximum. When W is at
maxima,
• - =0
• - =0
• - =0
• . =0 (6)
• From conservation of particles: =N and =0 (7)
• Similarly from the conservation of energy :
• =U and =0 (8)
• Now multiplying eq.No.7 by - eq.no.(8) by -and adding with equation 6 we get:
• - =0
• log -
• log = (9)
• = or ni=
• ni= (10)
• This equation is the Boltzmann distribution law; If T is absolute temperature and k is
Boltzman’s constant, then = & = log[{}3/2
Then eq. 10, becomes; ni= (10)
= ni= = (11)
Also, the energy distribution function of M-B statistics is given by,
f(E) = =
• The M-B statistics have the following limitations;
It is applicable only to an isolated gas of identical molecules which satisfies the conditions
1) The mean potential energy due to mutual interaction between the molecules very small compared
to their mean kinetic energy.
2) The gas should be dilute; The number of gas molecules per unit volume should be small; so that
the average separation between the molecules would be large; ( Under this condition the gas is said to
be degenerate);
The M-B statistics does not give correct expression for entropy S, of ideal gas, which leads to Gibb’s
paradox.
As per the expression for M-B statisics for an ideal gas the entropy gives negative value at zero
temperature. At T=0; S=negative which is not possible as per the third law of thermodynamics which
states that when the temperature of the system approaches absolute zero; the entropy approaches a
constant value S0.
It can not apply for indistinguishable particles.
 Maxwell’s statistical distribution law of velocity
• Let us consider an ideal gas contained in a container of volume V. Applying the
Maxwell-Boltzmann’s statistical distribution law,
• ni= = ni= where A= (1)
• If the particle is represented in Phase space with position co-ordinate x,y,z and
Velocity Vx, Vy, Vz; When the particle is moving to distance x to x+dx, y to y+dy, and
z to z+dz, the corresponding change in velocity can be represented by Vx to Vx+d Vx,
Vy to Vy+d Vy and Vz to Vz+d Vz;
• The number of particles within this phase volume dx.dy.dz. dVx. d Vy .d Vz is given
by, ni dx.dy.dz. dVx.dVy.dVz = dx.dy.dz. dVx.dVy.dVz (2)
• Here the Energy of the particle will be Ei= mV2 = m[Vx2+ Vx2 + Vx2] substituting in the
above equation:
• ni dx.dy.dz. dVx.dVy.dVz = dx.dy.dz. dVx.dVy.dVz (3)
• To evaluate the constant A, the eq.(3) can be integrated for all possible volume and
velocities;
• N=
•=
• = Volume of the container. Then
• N= AV
• = AV [. . ]
• Using the standard definite integrals, we have,
• = and = and
• =
• Then, N= AV []3/2 or A= []3/2 (4) where =
• Now substituting the value of A and in equation 3; we get,
• ni dx.dy.dz. dVx.dVy.dVz = dx.dy.dz. dVx.dVy.dVz (3)
• ni dx.dy.dz. dVx.dVy.dVz =dx.dy.dz. dVx.dVy.dVz (5)
• The number of molecules having velocity co-ordinates in the range Vx to
Vx+dVx, Vy to Vy+dVy and Vz to Vz+dV irrespective of the position co-ordinates
can be found by integrating the eq.(5) with respect to position co-ordinates;
which gives;
=ni dVx.dVy.dVz = dVx.dVy.dVz *V
ni dVx.dVy.dVz =N dVx.dVy.dVz (6)
Now if we find the number of molecules having velocity components in the
range Vx to Vx+dVx irrespective of Vy and Vz; This can be obtained by
integrating eq.6 with respect to Vy and Vz
n(Vx) dVx = N dVx. [dVy. dVz ]
• dVy = dVz =
• Then n(Vx) dVx = N dVx. [ ]
• n(Vx) dVx =N dVx. [ ]
• Then, n(Vx) dVx =N dVx. (7)
• Eq.7. gives the number of molecules having x-component of velocity in
the range between Vx to Vx+dVx. This equation shows that the velocity
component Vx is distributed symmetrically about the value Vx=0;
• The probability that a molecule will have x-component of velocity in the
range Vx to Vx + dVx is given by;
• P(Vx) dVx = = dVx.
• P(Vx) dVx = = dVx. (8)
• The above equation represents the Maxwell’s distribution of velocity.
• This can be expressed in terms of momentum P as:
• P(px) = dVx
• 1) The Maxwell’s distribution of velocity indicates that the probability function
(P(vx)) is symmetrically distributed about the value Vx=0; Also from the equation
it is clear that P(-Vx)= P(Vx); This also verifies the symmetric nature of P(vx))
• 2) The probability distribution function has maximum value for Vx for which

• =0 i.e. =0 i.e maximum value occurs when Vx= 0; So Pmax= So Pmax increases
asm increases and decreases as T decreases;
• 3) As the temperature increases the peak of Vx =0 lowers down with the wider
spread in the distribution curve; since the area under the curve is always same
as unity.
 T1
T1<T2<T3

T2

T3

P(Vx)
-Vx +Vx

Velocity distribution as per M-B statistics for different temperatures

 Quantum statistics
• Many of the Phenomenon such as black body radiation, photoelectric effect, Electron gas
movements in metals, etc. could not be satisfactorily explained by the M-B statistics; In
order to solve this problem energy distribution as discrete energy packets has been
employed in the quantum statistical methods; there are two different types of quantum
statistical distribution; Bose-Einstein and Fermi-Dirac statistical distribution.
• The minimum volume of a cell in phase space in quantum statistics will be equal to or
greater than h3; dx.dy.dz. dVx.dVy.dVz h3
• Consider two points arranging in two different cells using M-B, B-E, F-D statistics; In M-B
statistics, particles are distinguishable;
• In B-E statistics particles are indistinguishable but each cell may have any number.
• In F-D particles are indistinguishable and each cell contains only one representative point.
p q q p pq qp M-B

B-E

F-D
•
Minimum cell size in classical statistics and in quantum statistics
• The meaning of a single point distributed in minimum volume in phase space
can be understood by Heisenberg’s uncertainty principle.
• If dx is the size of the interval on the x axis and dPx is the momentum
coordinate, the area dx. dPx=h0 may be infinitesimally small as much as
possible in the case of classical statistics. This h0 can be expressed in
h0=length*momentum = (Length*Newton.sec)= Joule.sec.
• In quantum statistics, according to uncertainty principle the uncertainity in
position and momentum is not less than h. where h = 6.625*10-34 J.sec.
• So the minimum volume in quantum space = (dx.dy.dz)(dpxdpydpz.) = d>h3.
• The unit of (J.s)3
• Bose –Einstein statistics
• Fermi-Dirac statistics
 The quantum statistical theory consist of systems containing large numbers of identical
and indistinguishable particles represented by wave function for many body sate; 𝚿(, , ,
……….); where (, , , ……….) are the position vectors of first second, third particles.
Symmetric wave function: If on interchanging any pair of identical particles there is no
change in the sign of the wave function, they are symmetric
𝚿(, , , ……….) = 𝚿(, , , ……….) for symmetric; Their particles have spin angular momentum
zero or integral multiple of ℏ. Such particles are indistinguishable and is known as Bosons;
Bosons did not agree Pauli’s exclusion principle; So there is no upper limit for the number of
mesons in a cell; The bosons obeys Bose- Einstein statistics; Example: Photon, deuterons
mesons, etc.
Antisymmetric wave function: If on interchanging any pair of identical particles there is
change in the sign of the wave function, they are antisymmetric
𝚿(, , , ……….) = -𝚿(, , , ……….) for symmetric; They have spin angular momentum odd half
integral multiple of ℏ. i.e. (n+) ℏ; Such particles are called fermions; Fermions obeys Pauli’s
exclusion principle. So there is only one fermion in a given quantum state; Example: Electron,
positrons, neutrons;
 Bose-Einstein Distribution law

• Basic postulates of B-E statistics:

• In B-E statistics, the conditions are:
• 1) The particles of the system are identical and indistinguishable
• 2) Any number of particles can occupy in a single cell in phase space
• 3) The size of the cell can not be less than h3, where h is Plank’s constant.
• 4) The number of phase space cells are comparable with the number of
particles F(Ei) =
• 5) B-E statistics is only applicable to particles with spin angular momentum
zero or integral spin multiple of , which are called as Bosons;
Basic postulates of F-D statistics:

• In B-E statistics, the conditions are:

• 1) The particles of the system are identical and indistinguishable
• 2) Either no particle or single particle can occupy in a single cell in
phase space
• 3) The fermions obeys Pauli’s exclusion principle
• 5) B-E statistics is only applicable to particles with spin angular
momentum integral multiple of odd half integral spin;
 Bose-Einstein distribution law Fermi-Dirac distribution law
• Consider a system of N indistinguishable Boson • Consider a system of N indistinguishable
particles distributed in phase space, in k number Fermions distributed in phase space, different
of different compartments or energy levels. of boxes.
• In this n1 number of particles having energy E1. • In this n1 number of particles having energy E1.
• n2 number of particles having energy E2
• n2 number of particles having energy E2
and ni number of particles having energy Ei
and ni number of particles having energy Ei
• Now each energy levels Ei, there will be
different quantum states represented by gi. This • Now each energy levels Ei, there will be
gi represents the different degenerate states different quantum states represented by gi.
within the energy level Ei and is having the size This gi represents the different degenerate
of h3 states within the energy level Ei and is having
• Thus n1 number of particles having energy E1 the size of h3
and degeneracy g1 • Thus n1 number of particles having energy E1
• n2 number of particles having energy E2 and and degeneracy g1
degeneracy g2 • n2 number of particles having energy E2 and
and ni number of particles having energy Ei and degeneracy g2
degeneracy gi.
• ni number of particles having energy Ei and
degeneracy gi.
 B-E statistics
F-D statistics
Here, the total number of particles = n1+n2+n3+
………nk = (1) Here, the total number of particles =
n1+n2+n3+………ni = (1)
And total energy E=n1E1+n2E2+n3E3+
……………….nkEk = = Ei (2) And total energy E=n1E1+n2E2+n3E3+
……………….niEi = = Ei (2)
Now considering the i compartment. It has ni
th

indistinguishable particles distributed among its Now considering the i th

compartment. The
gi cells. Suppose that ni particles arranged in a first particle can be placed in any one of the
row and distributed among gi quantum states available gi state. The first particle can be
with gi-1 partitions in between. The total number distributed in gi different ways in accordance
of possible arrangements and particles is equal with Pauli’s exclusion principle and the
to total number of permutations of (ni+gi-1) remaining gi-1 will remain vacant. The second
objects in a row. The total possible ways of particle will be arranged in gi-1 different ways
arranging ni particles in gi-1 partitions = (ni+gi-1)! and the process continues. The total possible
ways of arranging ni particles in gi States with
2 4 2 4
1 1 energy Ei is given by: gi. gi-1. gi-2. gi-3..[gi-(ni)
3 3
gi
k =
i k i
• Omitting the meaningless • Omitting the meaningless
permutations due to the permutations that can be count two
times by shuffling the particles by
indistinguishable nature of the themselves, the thermodynamic
particles, the thermodynamic probability for ith cell will be:
probability Wi= • Wi=
• Similar expression will be obtained • Similar expression will be obtained for
for all other compartment, then the all other compartment, then the
thermodynamic probability : thermodynamic probability :
• W(n1,n2,..nk) = (3)
• W(n1,n2,..nk) = (3)
In equation (3) very large numbers
hence we we may neglet 1 in equation
3;
W(n1,n2,..nk) = (3)
 B-E statistics F-D statistics
Taking natural logarithm on both sides; Taking natural logarithm on both sides;
Ln (w)= - (4) Ln (w)= - (4)
Applying Sterling’s approximation: log x! Applying Sterling’s approximation: log x!=
= [xlog x]-x, the eq.4 becomes; [xlog x]-x, the eq.4 becomes;
Ln (w)= Ln (w)=
Ln (w)= Ln (w)=

The most probable distribution of the The most probable distribution of the particles
among the energy states in equilibrium is that
particles among the energy states in the probability of occurrence is maximum.
equilibrium is that the probability of When W is at maxima,
occurrence is maximum. When W is at
maxima,
 B-E statistics F-D statistics
• ln (ni+gi) + (ni+gi) * - ln ni – ni* =0
• -ln ni + (gi-ni) * +ln (gi – ni) =0
• ln (ni+gi) - ln ni =0
• =0
• =0 • =0
• -=0 • -=0
• Or =0 (6) • Or =0 (6)
• From conservation of particles: =N • From conservation of particles: =N and
and =0 (7) =0 (7)
• Similarly from the conservation of • Similarly from the conservation of
energy : energy :
• =U and =0 (8) • =U and =0 (8)
• Now multiplying eq.No.7 by eq.no. • Now multiplying eq.No.7 by eq.no.(8)
(8) by and adding with equation 6 we by and adding with equation 6 we get:
get:
B-E statistics F-D statistics
• + =0 • + =0
• ln • ln
• ln = -( (9) • ln= -( (9)
• ln = -( • = or
• = or • =
• = • =
• 1+ = • =
• = • ni= (10)
• ni= (10)
 B-E statistics B-E statistics

• This equation is the Bose- • This equation is the Fermi-Dirac

Einstein distribution law; If T is distribution law; If T is absolute
absolute temperature and k is temperature and k is Boltzman’s
Boltzman’s constant, then = & constant, then = & = log[{}3/2
= log[{}3/2 Also, the energy distribution
Also, the energy distribution function of M-B statistics is given
function of M-B statistics is given by,
by, f(E) = =
f(E) = =