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Lecture Notes - PH 301 & PH 401 - MODULE - 6 (Statistical Mechanics)
Lecture Notes - PH 301 & PH 401 - MODULE - 6 (Statistical Mechanics)
STATICAL MECHANICS
Up to the end of seventeenth century, all the observed physical phenomena were
explained by using either ordinary laws of mechanics or laws of electromagnetism. But
with the help of these ordinary laws, systems with many particles can’t be handled due to
mathematical complications. Moreover, in the last decade of seventeenth century there
were some ground-breaking experiments, such as black-body radiation, which needed new
theories for their explanation. As a result of these needs quantum theory came. When this
theory ties its knot with statistics, we get a new branch of physics known as Statistical
Mechanics capable of explaining the physical behaviour of all the systems whether
composed of a single particle or composed of a large number of particles.
Statistical mechanics is basically a formalism that aims at explaining the observed
physical properties of matter in bulk on the basis of dynamical behaviour of its microscopic
constituents. It is applicable to any physical system in any state whatsoever. It is not
concerned with the actual motion of the particles constituting a system; rather it
investigates some average or most probable properties of the system without going through
detail description of the constituent particles. It is noteworthy about statistical mechanics
that the larger is the number of particles in a mechanical system, the more correct are the
statistical predictions about the system and vice-versa. Before starting the various
formalisms in statistical mechanics, let us discuss a few general considerations regarding
the statistical nature of a macroscopic (observable with naked eyes) system.
Consider a H2 atom, which has the simplest atomic configuration with a single
electron revolving round the nucleus. The total energy of such an electron is given by
m e4
- , where m and e are mass and charge of the electron respectively, ε0 is the
8 0 h2 n2
permittivity of free-space, h is the Planck’s constant and n is known as principal quantum
number. Thus the total energy for such an electron solely depends on n. We know that for a
given value of n, we get other three quantum three quantum numbers whose values depend
on n in the following manner:
n-value l-value ml- value ms- value energy states no.of energy
states
1 1 1
- , {2,0,0, - }
2 2 2
2 0 0
1
{2,0,0, + } 2
2
1
{2,1,-1, - }
1 1 2
-1 - ,
2 2 1
{2,1,-1, }
2
1
{2,1,0, - }
0 2
1 1
- , 1
2 2 2 {2,1,0, }
1 2
1
+1 {2,1,+1,- }
1 1 2 6
- , 1
2 2 {2,1,+1, }
2
Thus for n = 2 energy level, we get eight distinct energy states. But all these eight energy
states have the same value of the total energy because, the total energy, as already stated,
depends only on the principal quantum number. Such type of distinct energy states having
the same total energy are known as degenerate states and it is said that the energy level n =
2 is 8-fold degenerate. Similarly we can show that n = 3 energy level is 18-fold degenerate.
Note that this type of degenerate states is direct consequence of the symmetry of the
respective system.
Where n i is the number of particles with energy i . Also the total number of particles is
N = n i ……………………………………………(7.2)
i
Under these conditions, a macrostate can be defined as the specification of the actual
values of the system parameters N,V and E.
At the microscopic level, however, there is a large number of independent
possibilities in which the macrostate(N,V,E) of the given system can be realized. In case of
a non-interacting system, since the total energy E consists of a simple sum of th N single-
particle energies i , there will obviously be a large number of different ways in which the
individual i can be chosen so as to make the total energy equal to E. In other words, for a
specific volume V of the system composed of specific number(N) of particles, there will
be a large number of different ways in which the total energy E of the system can be
distributed among the N particles constituting the system. Each of these (different) ways
specifies a microstate ( or, complexion) of the given system. Thus corresponding to a
particular macrostate, we have a large number of accessible microstates. At any time t , the
macrostate of the system is equally likely to be in any one of its microstates which are
consistent with the constrained conditions of the given system. This assumption forms the
very basis of statistical mechanics and is known as the postulate of “equal a priori
probabilities” for all accessible microstates of the system.
The total number of accessible (i.e., consistent with the constrained conditions of
the given system) microstates corresponding to a system (macrostate) is known as the
thermodynamic probability of the system and it is generally denoted by a symbol
Ω(N,V,E). There is a certain distinction between thermodynamic probability and
mathematical probability. Mathematical probability is always less than unity, whereas
thermodynamic probability (total number of microstates) is equal or more than unity. If S
represents the entropy of the system, S is related to Ω by the relation S = k loge Ω.
Phase Trajectory
r
Fig.7.1: Representation of phase points and phase trajectory in phase-space.
which is the volume of a phase cell( phase point) in phase-space. So the total volume of the
phase-space is
∫ ∫ ∫ ∫ ∫ ∫ dqx dqy dqz dpx dpy dpz
But ∫ ∫ ∫ dqx dqy dqz = ∫ ∫ ∫ dxdydz = given volume V of the particle. Thus the phase
dp
volume = V ∫ ∫ ∫ dpx dpy dpz. Now the volume of the momentum space containing
momentum between p and p+dp will be given by the volume of a spherical shell of radius p
and thickness dp. Therefore,
∫ ∫ ∫ dpx dpy dpz, = 4 p2dp
Thus the volume of phase-space = V. 4 p2dp
But the volume of a phase cell = h3
Therefore, total number of phase cells (microstates) in the momentum range from p to p+dp
is
V .4 p2 dp
g(p)dp = …………………………………………..(7.3)
h3
p2
If the energy corresponding to momentum p is E, E = or, p = 2mE
2m
m
dp = dE
2E
Thus total number of microstates in the energy range from E to E+dE is
1 m 1
g(E)dE = 3 V. 4 .(2mE). dE = 3 (4 V 2E m3/2)dE………………….(7.4)
h 2E h
Therefore total number of microstates (phase cells) per unit energy range
1
= 3 (4 V 2E m3/2)………………………………………………………………(7.5)
h
which gives the required density of states for a single particle.
[ Note: For particles having two allowed values of spin quantum number ms, the number of
available quantum states is 2 times that given by equations (7.3) and (7.4). Also for such
particles density of states becomes twice that given by eqn. (7.5).]
The various methods of statistical mechanics are applied to discuss some average or
most probable properties of large assemblies of electrons, atoms,molecules etc. Before the
advent of quantum mechanics, Maxwell, Boltzmann,gibbs etc, applied statistical methods
with the help of classical physics. These methods are collectively known as Classical
Statistics or Maxwell-Boltzmann (MB) Statistics.These statistics were proved to be
successful in explaining pressure, temperature etc. of gaseous systems. But these couldn’t
explain some experimental results like the energy distribution in case of black-body
radiation, specific heat at low temperatue etc. For explaining such phenomena Satyen Bose,
Albert Einstein, Enrico Fermi, Paul A. Dirac had made use of some new statics with the
help of newly discovered quantum theories. The new statistics are known as Quantum
Statistics and can be divided into following two categories:-
(i)Bose-Einstein (BE) statistics
(ii)Fermi-Dirac (FD) statistics
We’ll discuss the various interesting features of these three (MB,BE,FD) statistics
one by one in the following subsections.
N i E i = E………………………………………………(7.6)
i
N i = N ………………………………………………….(7.7)
i
The number of ways in which the groups of particles N1, N2,….., Ni could be
chosen from N particles is
N! N!
W1= = n …………………………….(7.8)
N1! N 2!...... N i ! !
Ni
i
ln W = N ln N – N + N i ln g i – N i ln N i N i
i i
N
= N ln N – N i ln i (using eqn.7.6) ……………………(7.12)
i gi
Now differentiating both sides we get,
N
d( ln W) = d(N ln N) - dN i ln i - N i d ln N i
i gi i gi
Ni
= - dN i ln - Ni d Ni
i gi i Ni
Ni
= - dN i ln - d Ni
i gi i
Ni
= - dN i ln …………………………………………...(7.13)
i gi
N i cons tan t , d N i 0
i i
For the most probable distribution, d( ln W)max = 0
N
Therefore dN i ln i = 0………………………………………………………...(7.14)
i gi
Since the system is in equilibrium, total number of particle and the total energy of the
system are constant. So,
Since d N i ’s are independent of one another, the above equation holds only if,
ln i E i = 0, or, N i g i e E i I
N
gi
Ni 1
ƒ(Ei) = = E i .................……………………..(7.18)
gi e
which physically gives the probability of a particle to occupy the energy state Ei.
Hence the total number of ways of the entire distribution of N particles in n number of
energy levels of the system is
n N g 1!
W= i i
……………………………………(7.20)
i N i !g i 1!
where denotes the product symbol.
If we assume that Ni and gi are very large, eqn. (7.120) reduces to
n N g !
W= i i
…………………………………………(7.21)
i !
Ni ig !
Taking natural logarithm of both the sides of eqn. (7.21) we get,
ln W = ln( N i g i )! ln N i ! ln g i !
i
= N i g i ln N i g i N i ln N i g i ln g i…………………(7.22)
i
(using Stirling approximation)
Now, differentiating eqn.(7.22) to obtain the most probable distribution, we get,
Since d N i ’s are independent of one another, the above equation holds only if,
g
ln N i g i ln N i Ei = 0 or, Ni =
i
………………………..(7.27)
e Ei 1
Hence the total number of ways for the entire distribution of N particles in n number of
energy levels of the system is
W=
n g i ! ……………………………………(7.30)
i N i !g i N i !
where denotes the product symbol.
Now taking natural logarithm on both sides of eqn.(7.30) and applying Stirling
approximation, we get,
ln W = ln g i ln N i ln g i N i
i
ln N i ln g i N i E i d N i 0 …………………………(7.35)
i
Since d N i ’s are independent of one another, the expression in the bracket of eqn.(7.35) is
zero for each Ni. Thus
gi
Ni …………………………………….(7.36)
e( E i ) 1
Hence the Fermi-Dirac distribution function is given by
Ni 1
ƒ(Ei) = ……………………………….(7.37)
g i e( E i ) 1
ƒ(Ei)
T1 T2>T1>0K
1
T = 0K
1
2
T2
0 Ei
Ei = EF
Case – 2 ( T> 0 K)
As the temperature increases beyond T= 0K, some of the electrons in the levels just
below the Fermi level go to levels just above EF resulting a gradual change in the
1 1
occupation index ƒ(Ei). If Ei = EF, ƒ(Ei) = 0 , i.e. at a finite temperature Fermi
e 1 2
energy of a system is that energy for which 50% energy states are filled and 50% states
are vacant.
1
g(E)dE = 2× 3
(4 V 2E m3/2)dE…………………………(7.40)
h
Hence the density of states g(E) for a Fermionic gas is given by
1
g(E) = 3 (8πV 2mE m)……………………………………(7.41)
h
which shows that g(E) depends only on E for a single type of fermionic gas kept in a
fixed volume V.
From fig.(7.3) it is obvious that at T = 0K, all the single-particle states upto energy
EF are filled up. Thus at T = 0K,
g ( E ) dE
N ( E ) dE
e 1
g ( E )dE [ e = 0]…………………..(7.42)
, i.e., total number of electrons is equal to the total number of single-particle energy
states, hence
EF
N = N ( E )dE
0
EF
= g ( E )dE [ using eqn.(7.42)]
0
16 2V m3 / 2 3/ 2
or, N = 3
……………………………………..(7.43)
EF
3h
which is the expression for the total number of electrons in the metal at T = 0K.
Therefore,
23
3N 2
EF = h ……………………….…………..(7.44)
8m V
which is the expression for Fermi energy of the electrons in the metal.
If n = N/V denotes the concentration of the electrons in the metal, the Fermi energy of the
electrons in the metal is
23
2
3n
EF = h ………………………………….(7.45)
8m
which shows the Fermi energy of the electrons depends solely on their concentration.
EF
E0tot = E.N ( E )dE
0
EF
E.g ( E )dE [ using eqn.(7.42)]
0
1 EF
= 3
(8 2V m3 / 2) E
3/ 2
dE [using eqn.(7.41)]
h 0
16 2V m3 / 2 5/ 2
= 3 EF
5h
3
= N E F [ using eqn.(7.43)] ………………(7.46)
5
which shows quantum effect because, classically the total energy of a system at
absolute zero is nothing but zero.
The average energy per electron at T = 0K can be written as
E 0tot 3
<E0> =
N 5
E F ………………………………….(7.47)
The number of photons having energy range between E to E+dE can be written
by using eqn.(7.27) as given by
g E
N ( E )dE ………………………………….(7.48)
E 1 dE
e
where g(E)dE is the number of states of photons having energy between E to E+dE.
In case of black-body radiation, the total number of particles is not conserved because,
photons are absorbed and re-emitted frequently by the walls of the chamber, i.e.
h
d …………………………………….(7.52)
dp =
c
Substituting the values of p and dp in eqn.(7.40), we get the number of quantum states
having frequency range between ν and ν+dν as
8 V
g ( )d 3 2 d …………………………………….(7.53)
c
Hence, expressing eqn.(7.38) in terms of ν we get,
N ( )d
g ( )d
.
8V 2 d
(using eqn.7.42)………………………..(7.54)
h / kT h / kT
e 1 3
c e 1
which represents the number of photons having frequency range between ν to ν+dν kept in
a chamber of volume V at temperature T.
Therefore, the energy density (total energy per unit volume) of the photons within
frequency range dν is given by
h h 8V 2 d
u ( )d N ( )d . .
V V c3 eh / kT 1
1
[ƒ(Ei)]MB = N i = E i
gi e
1
[ƒ(Ei)]BE = N i
gi
e Ei 1
1
[ƒ(Ei)]FD = N i
gi e ( E i ) 1
1
in above all the three cases β = .
kT
ƒ(Ei)
MB
+2 BE
+1
FD
0 (α+βEi)
-2 -1 0 +1 +2 +3
Fig. 7.4: Plot of distribution function ƒ(Ei) with (α+βEi) for the three statistics.
Thus in general the distribution function for all the three statistics can be written as
Ni 1
[ƒ(Ei)] = …………………………..(7.56)
g i e e E i kT
In statistical mechanics, the word ‘degeneracy’ is also used to indicate the deviation
from classical results, apart from its conventional meaning. The deviation from classical
N
results depends on the occupation index i as we have already shown in the previous
gi
section. A system is said to be
Ni
(i) strongly degenerate when »1 …………………………………….(7.57)
gi
Ni
(ii) weakly degenerate when >1 ………………………………………(7.58)
gi
Ni
(iii) non-degenerate when «1. ………………………………………(7.59)
gi
WORKED-OUT PROBLEMS
1. Find out the different macrostates and microstates of a system of three particles
distributed in three cells assuming the particles to be (i) indistinguishable, (ii)
distinguishable.
Soln.: Macrostate → specification of N,V,E
Microstate → specification of total number of ways corresponding to a specific
value of the set set {N,V,E}
Here, V, E are fixed. So macrostates and microstates would be determined only by N. For
indistinguishable particles (let,a,a,a) the all possible arrangements are shown below:
For distinguishable particles (let, a,b,c) the all possible arrangements are shown below:
2. Two particles are to be distributed in three cells. Find out the total number of possible
ways both from formula and in tabular form if the particles follow (i) MB statistics
(ii)BE statistics (iii) FD statistics.
Soln. The total number of possible ways (microstates) in MB, BE, FD statistics are
respectively given by
N!
g i N i , WBE =
N i gi 1! , g i !
N i !g i 1! N i !g i N i !
WMB = WFD =
Ni!
Here, N = 2, Ni = 2, gi = 3. Thus,
WMB =
2! 2
. 3 9 , WBE =
2 3 1! 4! 6 , W = 3! 3! 3
FD
2! 2! (3 - 1)! 2!2! 2! (3 - 2)! 2!1!
For MB statistics , the particles are distinguishable and any state can contain any number
of particles. Let the particles are a,b.
For BE statistics, the particles are indistinguishable and any state can contain any number
of particles. Let the particles are a,a.
CELL-1 CELL-2 CELL-3
aa 0 0
0 aa 0
0 0 aa
a a 0
a 0 a
0 a a
For FD statistics, the particles are indistinguishable and a single state can contain at best
one particle. Let the particles are a,a.
3. A system has non-degenerate single-particle states with 0,1,2,3 energy units. Three
particles are to be distributed in these states such that the total energy of the system is
3 units. Find the number of microstates if the particles obey
(i) MB statistics (ii) BE statistics (iii)FD statistics. Find the corresponding
macrostates and microstates also.
Soln.
(i) For MB statistics, let the three particles are A,B,C and the energy unit is E.
(ii) For BE statistics, let the three particles are A,A,A and energy unit is E.
(iii) For FD statistics, let the three particles are A,A,A and energy unit is E.
4. Calculate the density of states for an electron with energy 5eV constrained to move in
a cubical box of length 0.5 mm.
5. Calculate the probability of finding an electron with energy 6eV in an electron gas at
10000C if the Fermi energy of the gas is 5eV.
Soln. We know that the probability of finding an electron with energy Ei is given by
1
ƒ(Ei) =
Ei E F kT 1
e
Here, EF= 5eV = 5×1.6×10-19 Joule = 8×10-19 Joule
Ei = 6eV = 6×1.6×10-19 Joule = 9.6×10-19 Joule
k = 1.38×10-23Joule/Kelvin
T = 10000C = (273+1000) Kelvin = 1273 Kelvin
Thus
1 1 1
ƒ(Ei)= 9.11 1.105 104
9.6 10 8 10
19 19
e 1 9046.3
exp
1
1.38 10 1273
23
Soln. We know that the probability of finding an electron with energy Ei is given by
1
ƒ(Ei) =
Ei E F kT 1
e
0.01105
Here, ƒ(Ei) =
100
Therefore,
0.01105 1
=
100 9.6 1019 E F
exp 23
1
1.38 10 1273
which gives EF ≈ 8×10-19 Joule = 5eV and this is the required Fermi energy
of the gas.
8. Calculate the Fermi energy for metallic silver assuming each atom of silver contains
a single free electron.[ Given: Density of silver = 10.5 gm/c.c., atomic weight of
silver = 108]
EF = h 3n
2 23
=
6.61034
2
35.910 28
2/3
Joule
8m 8 9.11 1031 3.14
-19
= 8.8×10 Joule
8.8 10 19
= eV = 5.5 eV.
1.6 10 19
23
h 3n
2
EF = = 5.5 eV = 5.5×1.6×10-19 Joule
8m
= 8.8×10-19 Joule
or,
6.61034 2
3n
2/3
8.8 1019
8 9.11 10
31 3.14
On solving we get,
n ≈ 5.9×1028 per m3
which is the number of free electrons per unit volume of the metallic silver.
10. Calculate the total energy of an electron gas at absolute zero temperature for sodium
containing one free electron per atom.[ Given: Density of sodium = 9.7×103Kg/m3.,
atomic weight of sodium = 23].
EF = h
2
3n
=
23
6.610 34 3 2.5410 29
2 2/3
Joule
8m 8 9.11 1031 3.14
= 23.2×10-19 Joule
Hence the total energy per unit volume at absolute zero is
Etot
1
E 0tot 3 . N . E F 3 .n. E F
V 5 V 5
3
2.54 1029 23.2 1019 Joule/m3
5
= 35.36×1010 Joule/m3
11. Calculate the ground-state pressure of an electron gas for sodium containing one
free electron per atom. .[ Given: Density of sodium = 9.7×103Kg/m3.,atomic weight
of sodium = 23].
Soln. The Fermi energy(EF) and number density (n) of sodium is respectively given by
EF = 23.2×10-19 Joule
n = 2.54×1029 per m3
12. Show that sodium behaves as a metal in ordinary room temperature[ Given: Density
of sodium =9.7×103Kg/m3.,atomic weight of sodium = 23].
13. Show that the average momentum per electron at absolute zero temperature is
3
<p0> = p F , where pF is the Fermi momentum (i.e., momentum equivalent of
4
Fermi energy).
Soln. The total momentum of electrons in an electron gas at absolute zero(T = 0K)
temperature is given by
pF
p 0 tot = p.N ( p)dp ……………………………(7.60)
0
Soln. The number of photons per unit volume in the frequency range ν to ν+dν is
given by
8 2 d
N(ν)d ν = . [see eqn.(7.54)]
3 h / kT
c e 1
Therefore the total number of photons per unit volume having all possible energies
is
N = 8
kT x2 dx
x
hc 0 e 1
2
dx
From standard results we get, xx =2.405
0 e 1
3
1.38 10 231000
Therefore, N = 8 3.14 343 8
2.405
6. 610 10
= 2.045 1016 photons
which is the required number of photons per unit m3 at 1000 Kelvin.
15. Considering a relativistic particle (e.g. electron, proton etc.), calculate the density of
states .
Soln. We know that the number of quantum states in the momentum range from p to
p+dp is
V .4 p2 dp
g(p)dp = [see eqn.(7.3)]
h3
E2 = m02 c 4 p c 2 ……………………………….(7.68)
2
where, m0 is the rest mass of the particle and c is the speed of light in free space.
So, we can write from eqn.(7.68) that
p ( E 2 m02 c 4) / c 2 ……………………………..(7.69)
2
Hence the number of quantum states in the energy range from E to E+dE is
1/ 2
4V ( E m 0 c ) EdE
2 2 4
g(E)dE = 3 2
…………….(7.71)
h c c
So, the density of states is
g(E) =
4VE 2 2 4 1 / 2
3 3 E
h c
m c
0
for E ≥ m0 c2
ASSIGNMENTS
1. Calculate the number of possible ways by which three particles can be distributed
in thee cells following (i) MB statistics, (ii) BE statistics, (iii) FD statistics
[ Ans. MB – 27, BE – 10,FD – 1]
3. Consider a two particle system each of which can exists in states E1,E2 andE3.What
are the possible states if the particles are (i) bosons, (ii) fermions?
[Ans.BE – 6, FD – 3]
10. Using BE distribution law, deduce Planck’s law of black-body radiation and
11. If the density of zinc is 7130 kg/m3 and its atomic weight is 65.4, calculate its
Fermi temperature and hence prove that zinc is metal at ordinary room
temperature.[Given: the effective mass of a free electron in zinc crystal is
7.7×10-31 kg, Avogadro number = 6.023×1026atom/kg-atom.
[Ans.11.58×105K]
REFERENCES
1. Statistical Mechanics – Kerson Huang.
2. Statistical Mechanics – R.K. Pathria (Elsevier Publication)
3. Statistical Mechanics – Satyaprakash & Agarwal.
2.A coin and a six-faced dice are thrown. The probability that the coin shows head and
the dice shows 2 is
(i) ¼ (ii) 1/12 (iii) 1/6 (iv) 1/8
12.If Ni is the number of identical and indistinguishable particles in the ‘i’ th energy state
with degeneracy gi then classical statistics can be applied if
(i)
Ni = 1 (ii)
N i <<1 (iii)
N i >>1 (iv)gi = 0
gi gi gi
19. The Fermi temperature of a fermionic system with Fermi energy 1.38 eV is
(i)1.6×102 K (ii)1.6×104 K (iii) 1.6×106 K (iv)1.6×108 K