Review of Statistical Mechanics : Problem Sheet 01

January 31, 2018

All problems carry equal credits

1. The Gamma function in the integral representation is defined as
Z ∞
In = Γ(n + 1) = xn e−x .
0

Use integration by parts [or any other of your favorite tricks] to verify

Γ(n + 1) = nΓ(n).

• Integer : Verify I0 = I1 = 1.
It follows, that for integer n ≥ 0, Γ(n + 1) = n! (check).

√
• Half-Integer : Use properties of Gaussian integrals to obtain
√ Γ(1/2) = π.
Using Γ(n + 1) = nΓ(n), one similarly obtains Γ(3/2) = π/2 and so on.

• Negative Integer : Show that the Gamma function Γ(n) blows up for n ∈ {0, −1, −2, ...}.
Determine the character of pole at these points.
R∞
• The above expression can be written as In = nn+1 0 enf (y) dy. Obtain f (y).
• For large n, we can use the neighborhood of maximum of f (y) to approximate the integral.
Taylor expand f (y) around its maximum to verify the Sterling approximation.

2. Two systems with thermodynamic parameters (U1 , V1 , N1 ) and (U2 , V2 , N2 ) are brought together
to form a composite system. Obtain the equilibrium condition when these two systems are allowed
to
(i) Exchange energy and number of particles with each other
(ii)Exchange energy and volume with each other,
(iii) Exchange energy, volume and number of particles,
while treating the full system closed (not exchanging anything with outside).
3. Starting from the energy representation of the fundamental equation , i.e. U ≡ U (S, V, N ) and its
property that it is a homogeneous function of order unity show that the differential dependence
on the scaling parameter leads to the Euler equation of thermodynamics

T S − P V + µN = U.

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 Obtain the relation
dµ = vdp − sdT,
where v = V /N and s = S/N.
Also using Euler P
equation, show that the thermodynamic potential Gibbs free energy G is just µN
(or equivalently i µi Ni if there are more than one species of particles). Using, the previously
derive relation (Gibbs-Duhem relation) obtain the exact differential of G in terms of its variables
(or vice versa).

4. Let f (p; t) be giving the distribution of particles with momentum p. Starting from the definition
of the H− function, show that the equilibrium distribution corresponding to the conservation of
number of particles and total energy is the Boltzmann distribution. Obtain mean p, p2 and p2x
in a 3 − D space. What is the variance in momentum ?
5. A system of N localized magnetic ions is characterized by a Hamiltonian
N
X
H=D Si2
i

where Si is the spin of i − th ion which can take either of three values. (−1, 0, 1)

• Calculate the microcanonical entropy of the system, if the system is specified by energy E
• Obtain the specific heat per particle c as a function of T defined across different microcanon-
ical configuration. Plot c(T ).
• Obtain the partition function, if the system is brought into contact with thermal bath at
temperature T .
• Again obtain c(T ), in the canonical setting.
6. 1-D polymer with 2-D monomers: Consider a polymer formed by connecting N disc-shaped
molecules into a one-dimensional chain. Each molecule can align along either its long axis (of
length 2a) or short axis (length a). The energy of the monomer aligned along its shorter axis is
higher by  , that is, the total energy is H = U , where U is the number of monomers standing
up.
• Calculate the partition function, Z(T, N ), of the polymer.
• Find the relative probabilities for a monomer to be aligned along its short or long axis.
• Calculate the average length, hL(T, N )i, of the polymer.
• Obtain the variance, ∆L2 (T, N ).
• What does the central limit theorem say about the probability distribution for the length
L(T, N ) ?
7. Anisotropic oscillator : N distinguishable non-interacting particles are put in a 3-D anisotropic
oscillator potential
p2 p2 p2 ω 2 x2 ω2 y2 ω2 z2
H= 1 + 2 + 3 + 1 + 2 + 3 ,
2m 2m 2m 2 2 2

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 with eigen-energies
3  
X 1
En1 ,n2 ,n3 = ni + ~ωi
i=1
2

• Compute the average energy U (T, N ) for the system.

• Find the heat capacity C = (∂U/∂T )N in the high-temperature limit, i.e. kB T  ~ωi , ∀i.
8. Atomic spectral line : In 1916, Albert Einstein proposed that there are three processes oc-
curring in the formation of an atomic spectral line. The three processes are referred to as spon-
taneous emission, stimulated emission and photo absorption. With each is associated
an Einstein coefficient which is a measure of the probability of that particular process occurring.
Einstein considered the case of isotropic radiation of frequency ν and spectral energy density
ρ(µ). If N  1, identical atoms are in equilibrium with radiation in a cavity at temperature T .
Each atom has two energy eigenstates: the ground state with energy E0 and degeneracy g0 , and
excited state with energy E1 and degeneracy g1 , with E1 − E0 = hν. The processes which can
change the population of any states are following
• Spontaneous emission ∂n ∂n1



∂t spont = −A21 n2 = − ∂t spont
2

8πhν 3
• Stimulated emission ∂n ∂n1



∂t stim = −B21 n2 c3 (eβhν −1) = − ∂t stim
2

8πhν 3
• Photo absorption ∂n ∂n1



∂t Abs = B12 n1 c3 (eβhν −1) = − ∂t Abs
2

(a) Explain the dependencies of these processes on population, frequencies heuristically.

(b) At temperature T write down the expression for equilibrium.
(c) Obtain the ratios B21 /B12 and B21 /A21 .
9. Consider a system of N atoms (in a box of volume V ), each with intrinsic magnetic moment µ.
Let there be a magnetic field H switched on in the setting such that the angle between the field
and the orientation of i−th spin is αi , i.e.
X
H = Hf ree (q, p) − µH cos(αi )
i

∂M 
• Obtain the magnetic susceptibility per particle of the system, defined as χ = ∂H T where
i
M is the magnetization of the system M = − ∂hU
∂H .
• What is the T − dependence of the magnetic susceptibility at large T ? If you got it right,
it is the Curie’s law. Can you explain it intuitively ?
10. Non ideal gas : Once we are through with ideal gases, it is time to switch on interaction. A
crude way will be to use an effective approach for a single particle, in a mean field, approximating
the interaction and then go for N such independent particles. Let an atom be moving under
the influence of potential U0 (R) due to all others. Write down the expression for the classical
partition function.

• As a first approximation, the interaction is supposed to be infinitely large in some region

of volume and is replaced by a mean value Ū0 , in the remaining part. Write down the
expression for the partition function under this approach.

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• Next we calculate, the mean value of the potential. If ū is the mean interaction energy
between a pair, calculate the total energy for large N. Equating it with the total energy then
leads us to the mean value Ū0 , obtain its expression.
• Next step is to obtain the mean interaction energy between a pair. If u(R) is the inter-
action energy when two atoms are separated by distance R, obtain the mean interaction
energy (very crudely assuming every allowed distances outside R0 are equally probable),

d
with u(R) = RR0 . For sufficiently sharp fall-off we also assume d ≥ 3. If R < R0 , the po-
tential is supposed to blow up (Hard-ball approximation), making the region probabilistically
denied.
• Calculate the denied volume for a single particle in a system of N particles.
• Obtain the classical partition function, pressure of such a system and the equation of state.
Sounds familiar ?

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 Set 2

(a) Quantum Gas : Starting with the definition of Grand partition function
P
np =N
X X Y
Ξ(z, V, T ) = (ze−βEp )np ,
N =0 {np } p

where np is the number of particles with momentum p, show that the above expression can
also be rewritten as " #
Y X
−βEp n
Ξ(z, V, T ) = (ze ) .
p n

From this expression, obtain the equation of state for (i) Bosonic gas (ii) Fermionic gas.
(b) Quantum correlation : For the above system obtain the hnp1 i and the amount of quantum
correlation hnp1 np2 i − hnp1 ihnp2 i. Obtain the quantum correlation for a (bosonic) harmonic
oscillator system as well where p1 , p2 represent two different energy eigenstates.
(c) Cluster expansion and Virial coefficient : In cluster expansion, Grand partition func-
tion is expressed in terms of cluster integral bl as
1 1 X l
log Ξ = 3 bl z ,
V λ
l
p
where λ = 2π~2 /mkB T . Obtain the equation of state and the number density from this
expression. Relating the equation of state obtained from the virial expansion, obtain the
relations between the first four virial expansion coefficients and the first four cluster integrals.
(d) Phonons : A solid can be understood as a 3-D lattice, in which normal modes of the lattice
oscillation (a sound wave) in quantum mechanically give rise to phonons. With N atoms,
there will be 3N normal modes of oscillations. For large N and small lattice separation, the
k − space can be thought to be continuous. What will be the distribution function of the
normal modes in frequency (ω) space, where ω = kc for phonons ? For giving rise to total
3N normal modes, there must be a maximum frequency ωmax . Obtain, ωmax in terms of
the density N/V . Correspondingly, we will have a temperature (Debye Temperature) TD .
Obtain, the mean energy per phonon of the system and plot the specific heat as a function
of temperature, for T  TD and T  TD .
(e) Dirac fermions are non-interacting particles of spin 1/2. The one-particle states come in
pairs of positive and negative energies,
p
E± (k) = ± m2 c4 + ~2 k 2 c2 ,
independent of spins. For any fermionic system of chemical potential , show that the proba-
bility of finding an occupied state of energy µ+δ is the same as that of finding an unoccupied
state of energy µ − δ . ( δ is any constant energy.) Show that mean energy at finite temper-
ature satisfies, Z 3
d k E+ (k)
E(T ) − E(0) = .
2π 3 eβE+ (k) + 1
Obtain, CV for the massless Dirac fermion gas.

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(f) Variational method : The partition function corresponding to a Hamiltonian is formally
written as
Z = T r(eβH ).
Take the Hamiltonian of a system to be perturbed H0 → H(λ) = H0 +λ(H−H0 ). Obtain the
partition function for this perturbed system formally. What condition does the minimization
condition for log Z(λ) w.r.t. to λ formally give? Taylor expand log Z(λ) in λ to the leading
order to prove the Gibbs inequality
log Z(λ) ≥ log Z(0) − βhH − H0 iλ=0 .
(g) Virialization : In a system of N particles, acceleration of i−th particle due to Newtonian
gravitational pull of all other particles is given by
X Gmj (ri − rj )
r¨i = − .
|ri − rj |3
j6=i

Taking dot product of the above equation with respect to mi ri , prove the identity
 2 
1X d (ri · ri ) 1 X X Gmi mj
mi 2
− r˙i · r˙i =− .
2 i dt 2 i |ri − rj |
j6=i

Identify the total kinetic energy (T ) and potential energy (U ) of the system to write
1 X d2 (ri · ri )
mi − 2T = U.
2 i dt2
i ·ri )
Now, identify the term 21 i mi d(rdt
P
as a variable G(t) and show that for reasonable systems
the long time average of dG/dt vanishes, to write the Virialization equation
U + 2T = 0.
(h) A diatomic molecule is a collection of two atoms (of mass m1 and m2 ) bound together,
modeled by the Hamiltonian
p21 p2 1
H= + 2 + K(r1 − r2 )2 ,
2m1 2m2 2
where pi is the momenta of i−th atom and ri its radial location. Obtain the classical Grand
partition function of this diatomic gas put in a box of volume V and the equation of state.
At temperature T what is the mean separation between the atoms of this system ? [Hint :
Take large box approximation in the integration]
(i) A quantum harmonic oscillators is put in contact to a thermal bath at temperature T . The
thermal density matrix for such a system is given by,
r
mω mω 2 02 0
ρthermal (x, x0 ; β) = e− 2~ sinh β~ω [cosh β~ω(x +x )−2xx ] .
2π~ sinh β~ω
Using the relation for expectation of any operator Ô
hÔi = T r[Oρ],
get the expectations of x, p, x2 , (xp + px)/2 and p2 for a thermal harmonic oscillator.

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(j) A pair of harmonic oscillators are coupled linearly with each other with coupling strength λ

p21 p2 1 1
H= + 2 + mω 2 x21 + mω 2 x22 + λx1 x2 .
2m 2m 2 2
What is the ground state wavefunction ψ0 (x1 , x2 ) of such a system ? Show that the re-
duced density matrix (when one of the co-ordinate is traced over in the density matrix
ρ(x1 , x2 ; x01 , x02 ) = ψ0∗ (x1 , x2 )ψ0 (x01 , x02 )), can be cast into a thermal density matrix form.

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 Set 3

1. In the class we learnt to obtain the grand partition function of a photon gas. Use this to obtain the
temperature dependence of the pressure, entropy and the specific heat of the radiation. Cosmic
Microwave Background Radiation (CMBR) is afterglow of the big bang. Today this radiation
arrives to us with a reduced temperature of ∼ 3K. Obtain the force it would be exerting on you
(approximating yourself by a rectangle facing the radiation with a surface area of 1 m2 )1
2. Landau Diamagnetism : In presence of electromagnetic field, the momentum of an electron
gets corrected to
e
p → p − A.
c
If the vector potential is chosen to be A = Hxĵ, and the quantum eigenstate of the Hamiltonian
is chosen to be
ψ = eiky y eikz z φ(x),
show that the function φ(x0 ) with x0 = x−c~ky /eH satisfies the harmonic oscillator eigenequation
with a DC shift of ~2 kz2 /2m in energy eigenvalues

~2 kz2
 
1
 = (n, kz ) = + ~ωl n + ,
2m 2

where the frequency of this oscillator is the Larmour frequency ωl = |e|H/mc. Calculate the
grand partition function of the system if the degeneracy of a particular state is 2eHL2 /hc, with
L being side of a cubical box. At high temperature, obtain the magnetic susceptibility and see
this is negative !!

3. For spinless bosons in a container of volume V , show that the entropy and the specific heat above
the condensation temperature T0 ,
 
V 5 µ
S = kB 3 g5/2 (z) − g3/2 (z) ,
λ 2 kB T

and  
3 g5/2 (z) g3/2 (z)
cV = kB 5 −3 .
4 g3/2 (z) g1/2 (z)
Also obtain these thermodynamic quantities below the condensation temperature.

4. A two level bosonic system is described by energy spectrum

~2 k 2
j = k,σ = + 1 σ,
2m
where σ = 0, 1. Obtain the Bose-Einstein temperature of the system.
1 Don’t worry, we are not being pushed by the big bang after glow. Since the CMBR is isotropic, the net force is
anyway zero.

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5. Consider a gas of non-interacting fermions with an energy spectrum  = |p/~|s , contained in a
box of volume V . Writing
xm−1
Z
1
fm (z) = dx −1 x ,
m! z e +1
express the grand partition function in terms of fm (z). Calculate the quantities U/N, P and
number density n at zero temperature for the system.
6. Obtain the density matrix for these two different mixtures
(i) Equal mixtures of states |0i and |1i.
(ii) Equal mixtures of states √12 (|0i + |1i) and √12 (|0i − |1i) and show they are same. Therefore,
the mixed density matrix reflects unknowingness of an exact state.
A two particle quantum state is given as
X
|ψi = λi |ii1 |ii2 ,
i

where |ii is the basis elements corresponding to Hilbert space of two particles. Obtain the
reduced density matrix for particle 1 and 2. Argue why the von-Neumann entropy for each of
these particles (obtained from the reduced density matrix) is the same.
7. A Berthelot gas has an equation of state very similar to VdW gas
 a 
p+ (v − b) = RT
T v2
Obtain the critical parameters vc , Tc and pc . Express this system in terms of reduced quantities
and obtain the critical exponent β, γ and δ.
8. In the Curie -Weiss model the magnetization was obtained as

m = tanh(βH + βλm).

Obtain the asymptotic expression for the isothermal susceptibility a the critical temperature
for vanishing magnetic field. Obtain the spontaneous magnetization much below the critical
temperature and also when temperature approaches the critical value.