PH1002 (II Semester) : Dr. Ananta Charan Pradhan

PH1002 (II Semester)
Dr. Ananta Charan Pradhan
Department of Physics & Astronomy

NIT, Rourkela
March 15, 2021
Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Rourkela)
(II Semester) March 15, 2021 1 / 54
Statistical Mechanics: Introduction
What do we mean by Statistical Mechanics ?
Approach needed that enables statements about the system as a whole without
knowing the every single details.
Statistical mechanics is the formalism that tries to explain physical properties of
matter in bulk on the basis of the dynamical behavior of its microscopic constituents.
Where can we apply it ?

The range of it’s applicability is as wide as the range of natural phenomena.
In principal it is applicable to matter in any state whatsoever, for example
solid state, the liquid state, or the gaseous state, matter composed of several
phases and/or several components, matter under extreme conditions of density
and temperature, matter in equilibrium with radiation (as, for example, in
astrophysics), matter in the form of a biological specimen, and so on.
It can be applied to study matter in equilibrium as well as nonequilibrium state.

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Introduction
How do we proceed ?
We consider our system at hand having N(≈ 1023 ) number of particles confined
in a volume V . We carry out the analysis in the thermodynamic limit, i.e N →
∞, V → ∞ while the density n = N/V remains fixed and finite.
Next we consider the total energy E of the system. If the particles comprising the
system could be regarded as noninteracting, the total energy E can be written as
X
E= ǫi ni (1)
i
and X
N= ni (2)
i

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Introduction
Defining the macrostate of the system
The specification of the actual values of the parameters N, V , and E defines a

macrostate of the given system.
What are microstates of the system ?

The total energy E can be distributed among N particles in large number of ways.
Each of these (different) ways specifies a microstate.
The assumption :“equal a priori probabilities”

If there are no constraint then it is logical to assume that at any instant the system is
equally likely to be any one of these microstates. The actual number of microstates
is a function of N, V , E and can be written as W (N, V , E ). It’s remarkable that
complete thermodynamics of a system can be derived if one knows W (N, V , E ).
“Most probable microstate: If there are constraints– As the number of particles
increases, the most probable microstate of the system becomes more probable than
all of the other microstates combined.
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Introduction
Statistical distribution
Statistical mechanics deals with the behavior of systems of a large number of
particles. It does this by calculating the most probable behavior of the system
as a whole, rather than by being concerned with the behavior of individual
particles.
We find the most probable distribution for arranging the particles [n(ǫ), the
number of particles with the energy ǫ] in different available states yielding
particular distribution of energies.
The result is
n(ǫ) = g (ǫ) f (ǫ), (3)
where
g (ǫ) = number of states of energy ǫ

= statistical weight of the energy level ǫ
f (ǫ) = distribution function = avg . no of particles in the energy ǫ
= probability of occupancy of the energy state ǫ
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Statistical Distributions
Energy may be descrete or continuous. If the distribution of energies is

continuous, or at least can be approximated as being continuous, in that case, we
replace g (ǫ) by g (ǫ)dǫ, the number of states between g (ǫ) and g (ǫ) + dǫ.
There are three different kind of distribution corresponding to three different kind
of particles
1 Identical but distinguishable particles, the Maxwell-Boltzmann distribution.
Basically the classical statistics.
2Identical indistinguishable particles with integral spin, the Bose-Einstein
statistics.
3 Identical indistinguishable particles with half-integral spin, the Fermi-Dirac
statistics.
2 and 3 together constitute the quantum statistics.

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Statistical Mechanics
Maxwell-Boltzmann distribution
The Maxwell-Boltzmann distribution gives the average number of particles in the
energy ǫ at the absolute temperature T . It is given by
fMB (ǫ) = Ae −ǫ/kT (4)
The number n(ǫ) of identical and distinguishable particles is given by
n(ǫ) = Ag (ǫ)e −ǫ/kT (5)
A is like a normalization constant. We integrate n(ǫ) over all energies to get N, the
total number of particles. k is Boltzmann’s constant (1.38 × 10−23 J/K), and T is
the temperature in Kelvins.
Find relative number of atoms/molecules at various energy levels of a system at
equillibrium temperature T.

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Molecular Energies in an Ideal gas
Number of molecules with energies between ǫ and ǫ + dǫ
n(ǫ)dǫ = [g (ǫ)dǫ][f (ǫ)] = Ag (ǫ)e −ǫ/kT dǫ (6)

g (ǫ)dǫ, number of states that have energies between ǫ and ǫ + dǫ. ǫ in terms of
momentum p
p q
p = (2mǫ) = px2 + py2 + pz2 (7)
Think of as (px , py , pz ) forming a 3D grid in space. We count how many
momentum states there are in a region of space between p and p + dp (the
density of momentum states) and then transform to the density of energy states.

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Molecular Energies in an Ideal gas
Number of molecules with energies between ǫ and ǫ + dǫ

√
n(ǫ)dǫ = C ǫe −ǫ/kT dǫ (8)
3/2
Where C = 2m AB is a constant to be evaluated from the normalization
condition.
Normalization : ∞ ∞ √ −ǫ/kT
Z Z
N= n(ǫ)dǫ = C ǫe dǫ (9)
0 0
Z ∞ √
Γ(n) = e −x x n−1 dx, Γ(n + 1) = nΓ(n), Γ(n) = (n − 1)!, Γ(1/2) = π
0
2πN
From the integral the value of C = (πkT )3/2
Final molecular energy distribution:
2πN √ −ǫ/kT
n(ǫ)dǫ = ǫe dǫ
(πkT )3/2

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Average Molecular Energy
The total energy of N gas molecules

Z ∞ ∞
2πN
Z
E= ǫn(ǫ)dǫ = ǫ3/2 e −ǫ/kT dǫ (11)
0 0 (πkT )3/2
Using Gamma function the integral can be evaluated.
2πN 3 p 3
E =[ 3/2
][ (kT )2 (πkT )] = NkT (12)
(πkT ) 4 2
Average molecular energy ǭ = E /N = 32 kT
which is exactly the result you get from elementary kinetic theory of gases.
This is independent of the molecule’s mass.
ǭ at room temperature is about 40 meV, or (1/25) eV. This is not a large amount
of energy.

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MB Energy Distribution
Maxwell-Boltzmann energy distribution for the molecules of an ideal gas [n(ǫ)

2πN √ −ǫ/kT
Vs. (πkT )3/2
ǫe ].
The average molecular energy ǭ = 23 kT

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Distribution of Molecular Speeds
ǫ = 12 mv 2 → dǫ = mvdv
Now n(ǫ)dǫ = n(v )dv
we get the molecular speed distribution
m 3/2 2 −mv 2 /2kT
n(v )dv = 4πN[ ] v e dv (13)
2πkT

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1. Root Mean square speed (RMS Speed, v¯2 ) The proper way is to
average the squares of the velocities, and then take the square root of this value.
The resulting quantity is known as the root mean square (RMS) velocity
1 ∞ 2
Z Z ∞
m 3/2 4 −mv 2 /2kT
v¯2 = v n(v )dv = 4π[ ] v e dv (14)
N 0 0 2πkT
Using Gamma function √
for the integration, we get
v¯2 = 4π( 2πkT
m
)3/2 3 4 π ( 2kT
m )
5/2
= 3kT
m
r
3kT
vRMS =
m

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2. Average speed (v̄ )

The number of molecules with speeds between v and v+dv in a sample of N
molecules is given by
m 3/2 2 −mv 2 /2kT
n(v )dv = 4πN( ) v e dv (15)
2πkT
To find the average speed v̄ , we multiply n(v)dv by v, integrate over all values of
v from 0 to ∞ and then divide by N.
1 ∞
Z Z ∞
m 3/2 3 −mv 2 /2kT
v̄ = vn(v )dv = 4π( ) v e dv (16)
N 0 0 2πkT
Using Gamma function for the q integration, we get
m 3/2 1 2kT 2
v̄ = [4π( 2πkT ) ][ 2 ( m ) ] = 8kT
πm
q
v̄ = 8kTπm

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3. Most Probable speed (vp )

The number of molecules with speeds between v and v+dv in a sample of N
molecules is given by
m 3/2 2 −mv 2 /2kT
n(v )dv = 4πN( ) v e dv (17)
2πkT
To find the most probable speed vp , we set derivative of n(v) with respect to v to
zero and then solve the equation for v.
dn(v ) m 3/2 2 2
= 4πN( ) [(2v )e −mv /2kT − v 2 e −mv /2kT (2v )] = 0 (18)
dv 2πkT
Solving this, we get
r
2kT
vp =
m
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Ratio of the molecular

q speeds.
q q
3kT 8kT 2kT
vRMS : v̄ : vp = m : πm : m = 1.085 : 1 : 0.886
vRMS > vavg > vp
We know k = R/N,q M = q mN, Theqgas constant R = 8.314J/mol.K .
3RT 8RT 2RT
So, vRMS : v̄ : vp = M : πM : M

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Statistical Mechanics
Example 9.4: Find the rms speed of oxygen molecule at 0◦ C.

−27
m=(32 q
u)(1.66×10
q kg/u)=5.31×10−26 kg
3kT 3(1.38x10−23 )(273)
vrms = m = 5.31x10−26 = 461 m/s
Alternatively
q q
3RT 3x8.314x273
vrms = M = 32x10−3 = 460 m/s
Some more questions
1 Using the MB function, calculate the fraction of 40 Ar gas molecules with a
speed of 305 m/s at 500 K.
2 If the system in problem 1 has 0.46 moles of Ar gas, how many molecules
have the speed of 305 m/s ?
3 Calculate the values of vmp , vavg , and vrms for 132 Xe gas at 298 K. Show the
approximate locations of vmp , vavg , and vrms in the MB speed distribution
plot.
4 What will have a larger speed distribution, He at 500 K or at 300 K ? He at
300 K or Ar at 500 K ? Ar at 400 K or Ar at 1000 K ?

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Quantum Statistics
MB statistics (Classical systems): consists of identical and distinguishable particles. They are treated
like billiard balls.
FD and BE statistics (Quantum systems): containing large numbers of identical indistinguishable
particles.
If the de Broglie wavelength λ is much smaller than the average separation hdi of the particles, then we
can neglect the overlap of the de Broglie waves, in which case the particles can be treated as if they
were distinguishable: λ ≪ hdi where
h h h
λ= = √ = √ (19)
p 2mEk 3mkT
The average separation of the particles is hdi = (V /N)1/3 , where (N/V ) is the number of particles per
unit volume in the system.
Thus, √ h = (V /N)1/3 which when cubed and rearranged becomes
3mkT
N h3
( )( )≪1 (20)
V (3mkT )3/2
The condition under which the Boltzmann distribution can be used. Low particle densities and high
temperatures for particles of a given mass.

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Quantum Statistics
Bosons
The function f depends on whether or not the particles obey the Pauli exclusion
principle.
Bosons are particles with 0 or integral spin (0,1,2,3...).
Bosons do not obey exclusion principle.
The wave function of a system of bosons is not affected by the exchange of
any pair of them. The wave function of a system of bosons is symmetric.
Any number of bosons can exist in the same quantum state of the system.
Bosons obey Bose-Einstein statistics.
Fermions
Fermions are particles with odd half integral spins (1/2,3/2,5/2...).
Fermions obey exclusion principle.
The wave function of a system of Fermions changes upon the exchange of any
pair of them. The wave function of a system of Fermions is antisymmetric.
Only one fermion can exist in the same quantum state of the system.
Fermions obey Fermi-Dirac statistics.
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The three statistical distribution Functions

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Quantum Statistics
symmetric and antisymmetric wave functions
ψ(1), ψ(2), ψ(3),..... represents the wave function of the individual particles.
ψ(1, 2) represents the wave function of the two particles and can also be
written as ψ(1, 2) = ψ(1)ψ(2).
ψ(1, 2) = ψ(2, 1) −→ Symmetric wave function
ψ(1, 2) = −ψ(2, 1) −→ Antisymmetric wave function
Consider two identical particles (1 and 2) which may exist in two different
states (a and b). The wave function of the system is either
ψI = ψa (1)ψb (2) or ψII = ψa (2)ψb (1)
The particles are indistinguishable, so, we cannot tell whether ψI or ψII
describes the system. Both the states are equally likely or equivalently we can
say the system spends half the time in ψI state and half the time in ψII state.
Therefore a linear combination of ψI and ψII is proper description of the
system.

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Quantum Statistics
Bosons & Fermions: symmetric and antisymmetric wave functions
Two linear combinations are possible

1) Symmetric wave function(bosons)
1
ψS = √ [ψa (1)ψb (2) + ψa (2)ψb (1)] (21)
2
2) Antisymmetric wave function(fermions)

1
ψA = √ [ψa (1)ψb (2) − ψa (2)ψb (1)] (22)
2

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Quantum Statistics
Boson & Fermions: Special Cases
If both the particles be in the same state, say a
Case I: For distinguishable particles (classical case), both ψI and ψII become
ψM = ψa (1)ψa (2) (23)
(where the subscript M indicates Maxwell-Boltzmann statistics).
The probability density for distinguishable particles is
∗
ψM ψM = ψa∗ (1)ψa∗ (2)ψa (1)ψa (2) (24)
Case II: For bosons the wave function becomes
1 √
ψB = √ [ψa (1)ψa (2) + ψa (2)ψa (1)] = 2[ψa (1)ψa (2)] (25)
2
The probability density is
ψB∗ ψB = 2ψa∗ (1)ψa∗ (2)ψa (1)ψa (2) = 2ψM
∗
ψM (26)
If the particles are bosons, they are twice as likely to be in the same state as
distinguishable particles!
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Quantum Statistics
Boson & Fermions: Special Cases
Case III: For fermions the wave function becomes

1
ψF = √ [ψa (1)ψa (2) − ψa (2)ψa (1)] = 0 (27)
2
The probability density is
ψF∗ ψF = 0 (28)
If the particles are fermions, it is impossible for both particles to be found in the
same state.
Conclusions:
1 In a system bosons the presence of a particle in a particular quantum state
increases the probability that other bosons will be found in the same state.
2 In a system fermions the presence of a fermion in a particular quantum state
prevents other fermions from being in that state.

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Quantum Statistics
Bose-Einstein & Fermi-Dirac Distribution Functions
Bose-Einstein Distribution Function:
1
fBE (ǫ) = (29)
e α e ǫ/kT − 1
Fermi-Dirac Distribution Function:
1
fFD (ǫ) = (30)
e α e ǫ/kT + 1
and we know the Maxwell-Boltzmann Distribution:
α −ǫ/kT
fMB (ǫ) = Ae e (31)
fBE (ǫ) and fFD (ǫ) approaches fMB (ǫ) for ǫ >> kT

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Quantum Statistics
Fermi-Dirac Distribution Function

Fermi-Dirac Distribution Function
1
fFD (ǫ) = (32)
e α e ǫ/kT + 1
The Fermi energy ǫF is the energy at which fFD = 1/2. From the above equation we see that Fermi energy
ǫF = −αkT (33)
in terms of Fermi energy fFD becomes
1
fFD (ǫ) = (34)
e (ǫ−ǫF )/kT + 1
1 1 1
For T=0, ǫ < ǫF , fFD (ǫ) = = = 0+1 =1
e (ǫ−ǫF )/kT +1 e −∞ +1
1 1
For T=0, ǫ > ǫF , fFD (ǫ) = = e ∞ +1 =0
e (ǫ−ǫF )/kT +1
1 1
At T > 0, when E=EF we have fFD (ǫ) = =
e 0 +1 2

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Quantum Statistics
Distribution of fermions at different temperature
At absolute zero of temperature, the free electrons occupy different energy

levels continuously without any vacancy in between filled states.
Fermi energy is the highest energy state occupied by fermions at T=0.
Distribution of fermions will be different as keep on increasing the
temperature.

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Bose-Einstein condensate
When bosons get very cold, they all fall into the same (lowest) energy state.
Their wave packets merge and form a single wave packet. If the bosons are
atoms, the individual atoms lose their identity and form a super atom.
Eric A. Cornell and Carl E. Wieman and Wolfgang Ketterle won the 2001
Nobel prize for making a Bose-Einstein condensate out of 2000 rubidium
atoms.
They had to cool the atoms to 0.000001 K to do this.
One condensate in sodium contained about 5 millions atoms, was shaped like
a pencil of 8 micron across and 150 micron long and lasted for 20 sec.

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Black Body Radiation
We need to use Fermi-Dirac statistics to “explain” properties of metals and

semiconductors.
Bose-Einstein statistics “explains” blackbody radiation.
An ideal body or surface that completely absorbs all radiant energy falling
upon it with no reflection and that radiates at all frequencies with a spectral
energy distribution dependent on its absolute temperature
A blackbody is the best possible absorber / emitter of radiation.
The spectrum of blackbody radiation depends only on the temperature of the
blackbody.

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Black Body Radiation
To calculate the spectrum of radiation from

a blackbody, consider a box with a hole in it.
Radiation can get in the hole. It then
reflects back and forth inside the cavity.
A spherical cavity turns out to be the best
device for experimentally realizing blackbody
radiation
If the radiation interferes destructively, it
will never get out.
We only see radiation (waves) getting out
that were able to set up standing waves
inside the cavity.
Our job is thus to determine what kinds of
standing waves can exist in the cavity, and
what their energies are.

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Rayleigh-Jeans Formula
If the cavity is a cube L long on each edge, then the standing waves in the x, y, z
direction will be formed for the condition such that
2L
jx = λ =1,2,3,....=number of half wavelengths in x-direction.
2L
jy = λ =1,2,3,....=number of half wavelengths in y-direction.
2L
jz = λ =1,2,3,....=number of half wavelengths in z-direction.
Standing waves in a cubic cavity

2L 2
jx2 + jy2 + jz2 = ( ) (35)
λ
where jx =0,1,2,...., jy =0,1,2...,jz =0,1,2,...

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If j is
qa vector from the origin to a particular point jx , jy , jz then magnitude of
j = jx2 + jy2 + jz2
Total number of wavelengths between λ and λ + dλ is same as the number of

points in j-space whoes distance from origin lie between j and j+dj. Number of
standing waves
g (j)dj = (2)(1/8)(4πj 2 dj) = πj 2 dj (36)
We have j = 2L 2Lν
λ = c , dj = 2L
c dν
Number of standing waves
2Lν 2 2L 8πL3
g (ν)dν = π( ) dν = 3 ν 2 dν (37)
c c c
Density of standing waves in a cavity
1 8πν 2
G (ν)dν = g (ν)dν = dν (38)
L3 c3
The higher the frequency, the shorter the wavelength and the greater the number
of waves.
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We assume the waves originate in oscillators in the cavity walls and each oscillator
has two degrees of freedom. kT/2 is energy per degree of freedom. The energy
density in the frequency interval from ν to ν + dν is thus
8πν 2 kT
u(ν)dν = ǭG (ν)dν = kTG (ν)dν = dν (39)
c3
This is called the Rayleigh-Jeans formula which leads to the ”ultraviolet
catastrophe”. It predicts increasing energy density with increasing . It doesn’t
match experiment at all. It doesn’t even come close. Something is seriously
wrong.

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Fault of Rayleigh-Jeans formula
We found that the Rayleigh-Jeans formula could not explain the spectral
energy density for blackbody radiation.
What’s wrong with the Rayleigh-Jeans formula ?
Rayleigh divided up the energy into kT/2 for each degree of freedom. This is
fine for a continuous energy distribution (classical).
We now know that it doesn’t work for harmonic oscillators, where energy is
quantized in units of hν.
However, our density of standing wave modes is fine but our energy density
was wrong.

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Correction of Rayleigh-Jeans formula by Planck
Planck assumed that the oscillations in the cavity walls are limited to
ǫn = nhν.
Then he used Maxwell Boltzmann distribution to find that the number of
oscillation with energy ǫn is proportional to e −ǫn /kT at temperature T.
In such cases average energy per oscillator is
hν
ǭ = (40)
e hν/kT − 1

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Planck Radiation Law
Planck radiation formula = Energy of modes × Density of modes ×

Probability of occupancy of that mode
8πh ν 3 dν
u(ν)dν = hν G (ν)dν f (ν) = (41)
c 3 e hν/kT − 1
This formula works very well and it tells us that every body of condensed
matter radiates, regardless of its temperature. An object need not be so hot
that it glows conspicuously in the visible region in order to radiate.
The radiation from an object at room temperature is mainly in the far
infrared part of the spectrum to which eye is not sensitive.

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Wrong assumption in Planck Radiation Law
1 His assumption to use Maxwell Boltzmann distribution to find that the
number of oscillators.
2 Actual energy of oscillators is ǫn = (n + 1/2)hν not nhν. The zero point
energy of oscillator is 12 hν which cant be achieved by assuming MB statistics
for oscillators in the black body.
Correction:
3 Consider electromagnetic waves in the cavity as photon gas subject to
Bose-Einstein statistics since the spin of photon is 1. The value of α in BE
distribution function is zero due to nonconservation of photons.
4 Hence the photon distribution function is
1
f (ν) = (42)
e hν/kT −1
5 Ultimately the energy distribution of photons in the cavity is
8πh ν 3 dν
u(ν)dν = hνG (ν)f (ν)dν = (43)
c 3 e hν/kT − 1
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Wien’s Displacement Law
The wavelength (λmax ) at the peak of energy density of black body spectrum
at a given ‘T’ can be calculated by expressing ‘u’ as a function of ‘λ’ and
du
equating dλ to zero.
The energy distribution of photons in the cavity as a function of λ is
8πch 1
u(λ) = (44)
λ5 e hc/λkT − 1
Now the derivative,
!
1 −e a/λT ( Ta )( −1
λ2 )

d 1 1 −5 1
5
= 6
+ 5
= 0 (45)
dλ λ e a/λT −1 λ e a/λT −1 λ [e a/λT − 1]2
Simplifying this what we get is Wien’s displacement law

ch
= 2.898 × 10−3 m.K
λmax T = (46)
4.965k
Wien’s displacement law tells that the peak in the blackbody spectrum shifts
to shorter wavelengths as the temperature is increased.
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The Stefan-Boltzmann Law
The total energy density inside the cavity is found by integrating the energy
R∞ 3 4
density over all frequencies (standard integration used: 0 e xx−1 = π15 )
∞ ∞
8πh ν3 8π 5 k 4 4
Z Z
u= u(ν)dν = dν = T = aT 4 (47)
0 0 c 3 e hν/kT − 1 15c 3 h3
Where a is a constant. u ∝ T 4 . We expect energy R radiated by an object

per second per unit area is also proportional to T4 .
Stefan-Boltzmann law is given by
R = eσT 4 (48)
Where σ = ac −8 2 4
4 = 5.67 × 10 W /m .K . The emissivity e(0-1) depends on
the nature of radiation surface.
unity of radiation, R in the above equation is erg/cm2 /sec or joule/m2 /sec.

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1 How many independent standing waves with wavelengths between 9.5 and
10.5 mm can occur in a cubical cavity 1 m on a side ? How many with
wavelengths between 99.5 and 100.5 mm?
2 Find the radius of spherical blackbody that radiates 100 kW when its
temperature is 500 ◦ C.
3 The brightest part of the spectrum of the star Sirius is located at a
wavelength of about 290 nm. What is the surface temperature of Sirius?
4 A gas cloud in our galaxy emits radiation at a rate of 1.0x1027 W. The
radiation has its maximum intensity at a wavelength of 1 µm. If the cloud is
spherical and radiates like a blackbody, find its surface temperature and its
diameter.
5 Radiation from the Big Bang has been doppler-shifted to longer wavelengths
by the expansion of the universe and today has a spectrum corresponding to
that of a blackbody at 2.7 K. Find the wavelength at which the energy
density of this radiation is a maximum. In what region of the spectrum is this
radiation?

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Specific Heat of Solids
Dulong-Petit Law
The specific heat of a solid is the amount of energy required to raise its
temperature by 1 K.
We find specific heats by calculating the internal energy of solid as a function
∂E
of temperature. The specific heat = ( ∂T )V or P .
If we think atoms of a solid as 3-dimensional harmonic oscillators, each with
2 degrees of freedom, then the energy of a solid should be equal to
E = N × 3 × 2 × kT /2 = 3NkT = 3RT , where N = Avogadro’s number for 1
mole of solid and R is the gas constant = 8.31 J/mole.K =1.99 cal/mole.K.
The specific heat at constant volume is given by
∂E
CV = ( ∂T )V = 3R = 5.97 cal/mole.K
This is called Dulong-Petit’s law which states that the CV ∼ 3R for most of
the solids at room temperature.
The specific heat at constant pressure CP is 3 to 5 percent higher than CV in
solids because it includes the work associated with a volume change as well as the
change in internal energy.
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Limitations of Dulong-Petit Law
At high temperatures, all crystalline solids have a specific heat of 6 cal/(mole.K)
i.e., they require 6 calories per mole to raise their temperature 1 K which is
consistent with Dulong-Petit Law. However, Dulong-Petit Law completely failed
to explain two observations.
1 The CV of light elements such as boron, beryllium, and diamond (3.34, 3.85,
and 1.46 cal/(mole.K), respectively at 20 ◦ C).
2 Specific heat of solids drops sharply at low temperatures and approaches 0 as
T → 0 K.

Rourkela)
Einstein’s formula
Wrong assumption by Dulong-Petit: Assumption that average energy per
oscillator in solid is kT. This flaw is same as that responsible for the incorrect
Rayleigh-Jeans formula for black body radiation.
Correction by Einstein : Quantum statisics → The probability f(ν) that an
oscillator have frequency ν is f (ν) = ( hν1) .
e kT −1
Average energy per oscillator
hν
ǭ = hνf (ν) = hν (49)
e kT −1
Internal energy of solid
3Nhν
E = 3Nǭ = hν (50)
e kT − 1
Einstein’s specific heat formula
2 hν
∂E hν e kT
CV = = 3R hν (51)
∂T V kT (e kT − 1)2
Rourkela)
Case I: At high temperature, hν << kT →
hν hν 1 hν 2 hν 2
(e kT − 1)2 = [1 + ( )+ ( ) + .... − 1]2 = ( ) (52)
kT 2 kT kT
Specific heat becomes,
hν
3R[1 + kT + ....] hν 2 hν
CV = hν 2
( ) = 3R[1 + + ...] = 3R (53)
( kT ) kT kT
The Dulong-Petit value.

hν
Case II: At low temperature (i.e., as T → 0) e kT is very high as compare to 1. So,
the specific heat becomes,
hν
e kT hν 2 ( hν )2 ( hν )2
CV = 3R × hν × ( kT ) = 3R e hν/kT
kT
= 3R [1+ hν + 1 ( hνkT)2 + 1 ( hν )3 +...]
(e kT )2 kT 2 kT 6 kT
1
or CV = 3R [1/( hν )2 +1/( hν )+(1/2)+(1/6)( hν
)+...]
→ 0 as T → 0
kT kT kT

Rourkela)
( hν )2
Case III: At low temperature (but T > 0): 3R e hν/kT
kT
= 3R(θE /T )2 e −θE /T i.e,
as T << θE , CV is proportional to e −θE /T (where θE = hν k ). Thus specific
heat decreases as the temperature decreases. Good agreement with
experiment.
Conclusions: Specific heat decrease exponentially at low T’s, approaches to
classical value at high T and tends to zero at T=0.
Flaws of Einstein’s formula: The fall in specific heat with decrease in
temperature is more rapid than observed in experiment in case of some
elements (Cu, Al, etc.)
Why zero point energy of HO does not enter into the analysis ?
Ground state enrgy ( 12 hν) of HO is merely a constant and it is independent of
temperature. Added term to total energy will be ǫ0 = 3N( 12 hν) = a constant
∂E
and will vanish when the partial derivative ( ∂T )V is taken to find CV .

Rourkela)
The theory explained by Einstein is the first quantum theory of solids. He

made the simplifying assumption that all 3N vibrational modes of a 3D solid
of N atoms had the same frequency.
In this model, the atoms are treated as independent oscillators.
This refers to an isolated oscillator, but the atomic oscillators in a solid are
not isolated.They are continually exchanging their energy with their
surrounding atoms.
Debye theory gives right T-dependance of specific heats of solid (Cv ∝ T 3 )
incorporating the lattice vibrations (phonon) and their interactions.

Rourkela)
Question : Find the specific heat at constant volume of 1.00 cm3 of radiation in
thermal equilibrium at 1000 K.
Answer : Energy density u = aT 4
Stefan-Boltzmann law R = eσT 4
Stefan’s constant σ = ac −8
4 = 5.67 × 10 W /m .K
2
The total energy (U) is related to the energy density u by U=Vu, where V is the
volume. In terms of temperature, U = Vu = VaT4 = V 4σ c T
4
∂E
The specific heat at constant volume is then CV = ( ∂T )V = V 16σ
c T
3
16(5.67×10−8 )
3×108 (1000)3 (1.0 × 10−6 ) = 3.03 × 10−12 J/K

Rourkela)
Free Electrons in Metal
Specific Heat due to Electrons
Dulong-Petit, Einstein, and Debye theories exclude the contribution of free

electrons to the specific heat of solids.
In a typical metal each atom contributes one electron to the common
“electron gas”. If these electrons in solids behave like the molecules of an
ideal gas, each would have kT/2 of kinetic energy on the average.
The internal energy due to electrons for one mole of the metal would be
Ee = 23 NkT = 32 RT . The specific heat due to the electrons
∂Ee 3
CVe = ( )V = R (54)
∂T 2
The total specific heat should be CV = 3R + 23 R = 92 R but it is 3R at high
temperature. Why ?

Rourkela)
Density of States for free electrons in Metal
We need an expression for g (ǫ)dǫ, the number of quantum states available to

electrons with energies between ǫ and ǫ + dǫ.
We can use the same argument that we used to obtain the density of
standing waves in the black body of length L. The correspondence is exact
because there are two possible spin states, ms = + 21 and ms = − 21 , for
electrons, just as there are two independent directions of polarization for
otherwise identical standing waves.
We know g (j)dj = πj 2 dj, where j=2L. √
For an electron, λ =de Broglie wavelength= ph and p = 2mǫ.
√ q
2Lp
So, j = 2L
λ = h = 2L 2mǫ
h and dj = L
h
2m
ǫ dǫ
√ 3 3/2 √
g (ǫ)dǫ = 8 2πL h3
m
ǫdǫ
substituting V for L3 , Number of electron states
√
8 2πVm3/2 √
g (ǫ)dǫ = ǫdǫ
h3

Rourkela)
Free electrons in metal
Fermi Energy
From this density of states, we can calculate the Fermi energy (ǫF ). In
metals, electrons fill energy levels beginning with the lowest empty level and
proceeding to the highest.
In the ground state, there are no empty levels which have filled levels above
them. Electrons stop filling energy levels when we run out of electrons.
ǫF doesn’t depend on temperature, and only depends on how many electrons
are present in the given volume of metal. The total number of electrons in
the volume V is equall to the number of states since each state is limited to
one electron. So,
Z ǫF Z ǫF √ √
8 2πVm3/2 √ 16 2πVm3/2 3/2
N= g (ǫ)dǫ = ǫdǫ = ǫF (56)
0 0 h3 3h3
So, the Fermi energy
h2 3N 2/3
( ) ǫF = (57)
2m 8πV
where the quantity N/V is the density of electrons.
Rourkela)
Electron Energy Distribution in metal
Now we know the density of states, g(ǫ), we can calculate the distribution of
electron energies in a metal.
√ √ −3/2 √
(8 2πVm3/2 /h3 ) ǫdǫ (3N/2)ǫF ǫdǫ
n(ǫ)dǫ = g (ǫ)f (ǫ)dǫ = = (58)
e (ǫ−ǫF )/kT + 1 e (ǫ−ǫF )/kT + 1

Rourkela)
Rourkela)
Rǫ
The total energy E0 at T= 0 K is, E0 = 0 F ǫn(ǫ)dǫ
(Since at T = 0 K all the electrons have ǫ ≤ ǫF , e (ǫ−ǫF )/kT = e −∞ = 0)
3N −3/2 ǫF 3/2 3
Z
E0 = ǫ ǫ dǫ = NǫF (59)
2 F 0 5
3
Average electron energy at T = 0 is ǫ¯0 = ǫF
5
This average electron energy is on the order of a few eV. An effective temperature
calculated from ǫ = kT is on the order of many thousands of degrees for typical
metals.
The electronic heat capacity is proportional to kT/ǫF . This, plus the plot shows
why the electronic heat capacity is so low at ordinary temperatures.

Rourkela)
Free Electrons in Metal
Specific Heat due to Electrons

Why the free electrons in a solid do not contribute to the specific heat ?
Both the HOs of Einsteins model and the phonons of Debyes model are bosons and obey
Bose-Einstein statistics, which place no upper limit on the occupancy of a particular
quantum state.
But electrons are fermions, and obey Fermi-Dirac statistics. Only one electron of a metal
can occupy a given quantum state. Although at high T both systems of bosons and
fermions approach Maxwell-Boltzmann statistics but that temperature is not too high for
electrons around fermi level to contribute the CV of solid.
Example: The electrons to contribute to bulk specific heat, all the valence electrons would
have to receive energy from the nominal thermal energy kT. But The Fermi energy (≈ 0.5
eV) is much greater than kT (≈ 0.025 eV at room T and ≈ 0.043 eV at 500 K) and the
ovewhelming majority of the electrons cannnot receive such energy since there are no
available energy levels within kT of their energy.
The small fraction of electrons
2
which are within kT of the Fermi level does contribute a
small specific heat (CVe = π2 ( kT
ǫF
)R), and this electron specific heat becomes significant at
very low temperatures not at high temperature.

Rourkela)
Problems
1 Find the Fermi energy in copper on the assumption that each copper atom
contributes one free electron to the electron gas. The density of copper is
8.94x103 kg/m3 and its atomic mass is 63.5 u.
Answer:
The electron density N/V in copper is equal to the number of copper atoms
per unit volume.
N atoms mass/m3 8.94×103 28
V = m3 = mass/atom = 63.5×1.66×10−27 = 8.48x10 atoms/m3 =
28
8.48x10 electrons/m3
h2 3N 2/3
The Fermi energy, ǫF = 2m ( 8πV ) ,
where the quantity N/V is the density of electrons.
(6.62×10−34 )2 3×8.48x1028 2/3
ǫF = 2×9.11×10 −31 ( 8π ) = 1.13 × 10−18 J = 7.04eV
2 The Fermi energy in silver is 5.51 eV. (a) What is the average energy of the
free electrons in silver at O K ? (b) What temperature is necessary for the
average molecular energy in an ideal gas to have this value? (c) What is the
speed of an electron with this energy?

Rourkela)

PH1002 (II Semester) : Dr. Ananta Charan Pradhan

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PH1002 (II Semester)

Dr. Ananta Charan Pradhan

Department of Physics & Astronomy

March 15, 2021

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

What do we mean by Statistical Mechanics ?

Where can we apply it ?

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

The specification of the actual values of the parameters N, V , and E defines a

What are microstates of the system ?

The assumption :“equal a priori probabilities”

g (ǫ) = number of states of energy ǫ

Energy may be descrete or continuous. If the distribution of energies is

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

fMB (ǫ) = Ae −ǫ/kT (4)

The number n(ǫ) of identical and distinguishable particles is given by

n(ǫ) = Ag (ǫ)e −ǫ/kT (5)

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

n(ǫ)dǫ = [g (ǫ)dǫ][f (ǫ)] = Ag (ǫ)e −ǫ/kT dǫ (6)

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Number of molecules with energies between ǫ and ǫ + dǫ

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Average Molecular Energy

The total energy of N gas molecules

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Maxwell-Boltzmann energy distribution for the molecules of an ideal gas [n(ǫ)

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Distribution of Molecular Speeds

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Distribution of Molecular Speeds

2. Average speed (v̄ )

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

3. Most Probable speed (vp )

Ratio of the molecular

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Example 9.4: Find the rms speed of oxygen molecule at 0◦ C.

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

symmetric and antisymmetric wave functions

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Bosons & Fermions: symmetric and antisymmetric wave functions

Two linear combinations are possible

2) Antisymmetric wave function(fermions)

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Boson & Fermions: Special Cases

Case III: For fermions the wave function becomes

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Fermi-Dirac Distribution Function

in terms of Fermi energy fFD becomes

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

At absolute zero of temperature, the free electrons occupy different energy

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

We need to use Fermi-Dirac statistics to “explain” properties of metals and

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

To calculate the spectrum of radiation from

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002

Standing waves in a cubic cavity

Dr. Ananta Charan Pradhan (Department of Physics & AstronomyNIT,PH1002