Oefeningen Statistical Mechanics

Alexander Mertens
Fysica
January 8, 2016
Intro
This text contains solutions to the notes of Statistical Mechanics by E. Car-
lon (2014). All of these solutions are written by students, so dont take any
results in here at face value. I happily receive any corrections or suggestions
for the solutions at alexander@wina.be. Any solutions you would like to add
to this text, you can send to that same email. Thanks to Quentin Decant
for his corrections.

1
Contents
0 A Brief Review of Thermodynamics 4
0.1 Internal Energy of Ideal Gas . . . . . . . . . . . . . . . . . . . 4
0.2 Adiabatic transformation for an ideal gas . . . . . . . . . . . 4

1 Random walks, diusion and polymers 5

1.1 One dimensional random walk . . . . . . . . . . . . . . . . . . 5
1.2 Diusion with an absorbing boundary . . . . . . . . . . . . . 5
1.3 Diusion with a reflecting boundary . . . . . . . . . . . . . . 6
1.4 Fluorescence recovery after photobleaching . . . . . . . . . . 7
1.5 Reaction-diustion equation: a simple example . . . . . . . . 8
1.6 Radius of gyration of a polymer . . . . . . . . . . . . . . . . . 8

2 Ensembles in Classical Statistical Mechanics 11

2.1 Surface and Volume of a high dimensional sphere . . . . . . . 11
2.2 Ideal gas in the microcanonical and canonical ensemble . . . 12
2.3 Harmonic oscillators in the microcanonical and canonical en-
semble . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.4 Maxwell speed distribution . . . . . . . . . . . . . . . . . . . 16
2.5 Ideal gas in a gravitational field . . . . . . . . . . . . . . . . . 19
2.6 Energy fluctuations in an ideal gas . . . . . . . . . . . . . . . 21
2.7 Generalized equipartition theorem . . . . . . . . . . . . . . . 22
2.8 Harmonic Oscillator in polar coordinates . . . . . . . . . . . . 23
2.9 Diatomic molecules (1) . . . . . . . . . . . . . . . . . . . . . . 25
2.10 Diatomic molecules (2) . . . . . . . . . . . . . . . . . . . . . . 26
2.11 Langevins theory of paramagnetism . . . . . . . . . . . . . . 28
2.12 Van Leeuwens theorem . . . . . . . . . . . . . . . . . . . . . 30
2.13 Stretching DNA . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.14 Stretching a polymer: the low force limit . . . . . . . . . . . . 33
2.15 Worm like chain . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.16 Stretching a gaussian polymer . . . . . . . . . . . . . . . . . . 34
2.17 Rigid monomeric chain . . . . . . . . . . . . . . . . . . . . . . 37
2.18 Solid-Gas equilibrium . . . . . . . . . . . . . . . . . . . . . . 38
2.19 Ideal gas in grand canonical ensemble . . . . . . . . . . . . . 40
2.20 Coexisting phases . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.21 Arrhenius law . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

2
3 Interacting Systems 45
3.1 Hard Rods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.2 Hard Disks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.3 Virial expansion for Hard Spheres . . . . . . . . . . . . . . . . 48
3.4 Second virial coefficient and the Boyle temperature . . . . . . 50
3.5 Virial coefficient . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.6 Second virial coefficient of Argon . . . . . . . . . . . . . . . . 51
3.7 The Flory exponent of a polymer . . . . . . . . . . . . . . . . 53
3.8 The mean field theory of non-ideal gases . . . . . . . . . . . . 53
3.9 The critical exponents of a van der Waals fluid . . . . . . . . 55
3.10 One dimensional Ising model . . . . . . . . . . . . . . . . . . 55
3.11 The Infinite-range Ising-model . . . . . . . . . . . . . . . . . 56
3.12 The mean field solution of the Ising model . . . . . . . . . . . 57

4 Quantum Statistical Mechanics 58

4.1 Quantum Harmonic Oscillators . . . . . . . . . . . . . . . . . 58
4.2 Low temperature limit of a quantum partition function . . . . 59
4.3 Ideal gas with internal degrees of freedom . . . . . . . . . . . 60
4.4 When are quantum eects important? . . . . . . . . . . . . . 61
4.5 Bose-Einstein, Fermi-Dirac and Maxwell-Boltzmann statistics 61
4.6 Quantum Corrections in a Bose ideal gas . . . . . . . . . . . 62
4.7 Bose-Einstein condensation in two dimensions? . . . . . . . . 63
4.8 Bose condensation in a band . . . . . . . . . . . . . . . . . . 64
4.9 Bose-Einstein condensation in a harmonic potential . . . . . . 64
4.10 Photons and phonons are bosons . . . . . . . . . . . . . . . . 65
4.11 Black body radiation . . . . . . . . . . . . . . . . . . . . . . . 65
4.12 Phonons on a String . . . . . . . . . . . . . . . . . . . . . . . 67
4.13 Debye Model . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4.14 Ideal Fermi gas in two dimensions . . . . . . . . . . . . . . . 67
4.15 Landau Theory of diamagnetism . . . . . . . . . . . . . . . . 67
4.16 Pauli spin paramagnetism . . . . . . . . . . . . . . . . . . . . 67
4.17 Particles in magnetic field . . . . . . . . . . . . . . . . . . . . 67
4.18 High temperature specific heat of metals: a paradox? . . . . . 68
4.19 Electronic contribution of specific heat . . . . . . . . . . . . . 68
4.20 White dwarfs . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

3
0 A Brief Review of Thermodynamics
0.1 Internal Energy of Ideal Gas
The first law states dE(S, V ) = T (S, V )dS P (S, V )dV . From this we
derive

dF = d(E T S) = SdT P dV

This gives us

@F
= S
@T V
@F
= P
@V T

Dierentiating the last expression with respect to V gives us

@S @ @F
=
@V T @V @T V T

@ @F
=
@T @V T V
@P
=
@T V

And so we see
dE @E @E @S
= +
dV @V S @S V @V T
@P
= P +T
@T V
N kb
= P +T
V
=0

0.2 Adiabatic transformation for an ideal gas

4
1 Random walks, diusion and polymers
1.1 One dimensional random walk
Call the probability that you take a step sn to the right pR .

a) The probability that the walk

of N steps performs n steps to the right
N
is equal to P (n, N ) = pnR (1 pR )N n .
n

b) Consider the function

N
X N
f (N, x, y) = xn y N n
n
n=0
= (x + y)N

Now notice that

@f (N, x, y)
N x(x + y)N 1
=x
@x
N
X N
= nxn y N n
n
n=0

So we have N pR = pR @f (n,x,y)
@x = hni. In the same way
x=p
R ,y=1 pR
2 @ @f (n,x,y)
we have hn i = pR @x x @x = N pR + N (N 1)p2R .
x=pR ,y=1 pR
The variance is then Var(n) = N pR N p2R = N pR (1 pR ).
PN
c) Now call x = n . We see hxi = N hs0 i = 0. We also find
n=0 sP
P
hx i = n,m hsn sm i = N
2 2 2 2
n= hsn i = N hs0 i = N (pR + (1 pR )2 ).

1.2 Diusion with an absorbing boundary

a) If we mirror the solution by putting the same amount of particles but
negative at the beginning at x0 , so c(x, 0) = N ( (x x0 ) (x + x0 ))
and do not impose that the particles be absorbed. We see that any of
the particles arriving from the right, will be cancelled by the negative
particles coming from the left. The solution is the sum of the two
gaussians

5

N (x x0 )2 (x + x0 )2
c(x, t) = p exp exp
4Dt 4Dt 4Dt

Now if we only take the right part of this solution, and let for every
x < 0 the solution be zero, we have the solution to our original prob-
lem.

b) Using the taylor expansions of the exponentials we see

N (x x0 )2 (x + x0 )2
c(x, t) = p + + O(x4 )
4Dt 4Dt 4Dt
N
= p 4xx0 + O(x4 ) .
4Dt 4Dt
So c(x, t) vanishes linearly around x = 0.

c) The total number of particles at some time t is equal to

Z +1
N (t) = c(x, t)dx
0
Z +1
N (x x0 )2 (x + x0 )2
=p exp exp dx
4Dt 0 4Dt 4Dt
Z +1 Z +1
N x2 x2
=p exp dx exp dx
4Dt x0 4Dt x0 4Dt
Z x0 Z +1
N x2 x2
=p exp dx exp dx
4Dt 1 4Dt x0 4Dt

1.3 Diusion with a reflecting boundary

We have a similar situation as in the previous exercise, consider the begin
situation that N particles start at x0 and x0 . Now each time a particle
arrives from the right to go to left, a particle will arrive from the left to go
to the right, as if the particle from the right bounces back. The solution is

N (x x0 )2 (x + x0 )2
c(x, t) = p exp + exp .
4Dt 4Dt 4Dt
We have

6

@c(0, t) N (x x0 ) (x x0 ) 2 (x + x0 ) (x + x0 )2
= p 2 exp 2 exp
@x 4Dt 4Dt 4Dt 4Dt 4Dt x=0
= 0.

At some point t0 , we have c(0, t0 ) = c(x0 , t0 ), so

x20 x20
2 exp = 1 + exp
4Dt0 Dt0

x20
Denote with x = exp 4Dt0 , then we solve the following equation

1 2x + x4 = 0

This equation has two real solutions, x1 = 1 and x2 1/2. If x = 1, then

x20
t0 ! 1 but in the other case we have t0 = 4D log x2 .

1.4 Fluorescence recovery after photobleaching

The general solution is given by

Z
c(x, t) = dyc(y)Gy (x, t).

So in this case we have

Z a Z +1
c0 (x y)2 (x y)2
c(x, t) = p exp dy + exp dy .
4Dt 1 4Dt a 4Dt

So at x = 0 and for t > 0, we see

Z a
1 y2
c(0, t) = c0 1 p exp dy .
4Dt a 4Dt

For the half-recovery time we have

Z a
1 y2
c0 1 p exp dy = c(0, ) = c0 /2
4D a 4D

7
In other words
Z a
1 1 y2
=p exp dy
2 4D a 4D
Z a/p4D
1
=p exp( u2 )du
a/p4D

a
= Erf p
4D
1 2, D a2
Now if we define = (2 Erf (1/2)) we find that = a2
or D = .

1.5 Reaction-diustion equation: a simple example

Notice that
@ 2 g(x, t) t @
2 c(x, t)
D = De
@x2 @x2
@c(x, t)
= e t
@t
and
@g(x, t) t @c(x, t)
= g(x, t) + e
@t @t
holds.
Thus we can conclude
@g(x, t) @ 2 g(x, t)
=D g(x, t),
@t @x2
so g(x, t) satisfies equation (1.7.4).

1.6 Radius of gyration of a polymer

Notice that
i
X
xi = x0 + ri .
k=0

We also see that the following holds

8
 N
X
(N + 1)Rg2 = x2i + x2CM 2xi xCM .
i=0

P D PN E
We know that N hx i x CM i = x CM x i = hxCM (N + 1)xCM i =
2 i=0 i=0
(N + 1) xCM , so we see

* N
+
X
(N + 1)Rg2 = (x2i (N + 1)x2CM )
i=0
*N +
X 1 X
= (x2i ) xi xj
N +1
i=0 i,j
* + * +
1 X 1 X
= (x2i + x2j 2xi xj ) = (xi xj )2 .
2(N + 1) 2(N + 1)
i,j i,j

Using the previous relation we find

* i j
!2 +
X X X
(N + 1)2 Rg2 = rk rk ,
i<j k=0 k=0

where we have dropped the factor 2 because we only sum over i < j. Further
we calculate
* j
!2 +
X X
2 2
(N + 1) Rg = rk
i<j k=i+1

X j
X j
X
= hrk rl i ,
i<j k=i+1 l=i+1

When k 6= l, the random variables rk and rl are independent of each other.

9
So hrk rl i = a2 k,l . Continuing the calculation we see
j
X X j
X
2
(N + 1) Rg2 = a2 k,l
i<j k=i+1 l=i+1
j
X X
= a2
i<j k=i+1
j 1
N X
X
2
=a (j i)
j=0 i=0
N
X
2 2 j(j 1)
=a j
2
j=0
N
a2 X 2
= (j + j)
2
j=0
2
a N (N + 1)(N + 2)
= .
6
So we conclude
a2 N (N + 2)
Rg2 =
6(N + 1)

10
2 Ensembles in Classical Statistical Mechanics
2.1 Surface and Volume of a high dimensional sphere
a)
Notice that

Z
2
IN = dN xe x
Z Z Z P 2
= . . . dx1 dx2 . . . dxN e i xi

Z Z Z
2 2 x2N
= dx1 e x1 dx2 e x2 . . . dxN e
Z N
x21
= dx1 e

= I1N .
R x2 p
The gaussian integral dxe is equal to , so IN = N/2 .

b)
Denote with AN the surface of dimension N with radius 1. We find that if
we convert to polar coordinates

Z 1Z
r2
IN = rN 1
e drd
0 A
Z N1
r2
= N 1 rN 1
e dr
0

Now substitute with u = r2 , so rN 1 = uN/2 1/2 and du = 2u1/2 dr. We

conclude

Z 1
N 1
IN = uN/2 1
e u
du
2 0
N 1 (N/2)
=
2
2 N/2
So we conclude N 1 = (N/2) .

11
c)
2 2 2 3/2 3/2
We find that 1 = (1) = 1! = 2 and 2 = (3/2) =4 (1/2) = 4.

2.2 Ideal gas in the microcanonical and canonical ensemble

a)
Notice

Z
1
(E, N, V ) = P dp1 . . . dpN V N
N !h3N p2i /2m<E
Z
V N (2m)3N/2
= p du1 . . . duN .
N !h3N S3N ( E)
p
where we used the substitution ui = pp2m
i
and S3N ( E) denotes a sphere
p
in 3N dimensions with radius
p E. The last integral is just the volume of
the 3N sphere with radius E so

V N (2mE)3N/2
(E, N, V ) =
N !h3N (3N/2 + 1)
N
V 4mE 3N/2 5N/2
e ,
N 3N

where we used N ! N N e N . The microcanonical density of states is just

partial derivative of the microcanonical phase space with respect to E. So
we see
@(E, N, V )
!(E, N, V ) =
@E

3 N 1 N 4m 3N/2 3N/2 1 5N/2
= V N E e .
2 3N

b)
The entropy is equal to

V 3N 4mE 5N
S(E) = kB N log + log + .
N 2 3N 2

12
We also see that

3 3N 4mE 5N
log !(E, V, N ) = (log N log V N log N + log N + log log E +
2 2 3N 2
S(E)
.
kB

c)

S(E, V, N ) V 3N 4mE 5N
= N log + log +
kB N 2 3N 2

= S(E, V, N ).
kB

d)
Notice
@S
P =T
@V E,N
N
= T kB ,
V
so P V = N kB T , which is precisely the ideal gas law. We also see that

1 @S
=
T @E V,N
3N
= kB ,
2E
3N kB T
so E = 2 .

e)
We calculate the partition function as follows

Z1N
ZN =
N!
3N/2
2m
VN
= .
N!

13
This gives us
@ZN
E=
@
3N
= ,
2
3N kB T
or E = 2 .

2.3 Harmonic oscillators in the microcanonical and canonical

ensemble
a)
pm
Consider the substitution ui = ppi and vi = !i qi , so we see
2m 2

Z
1
(E, V, N ) = P p2 m! 2 q 2
dp1 . . . dpN dq1 . . . dpN
N !h3N i
i 2m +
i i <E
2
p N
(2m)N/2 2/m Y 2 1
= !i (E)N
N !h3N N!
i
Y
N 2N 2N
(2E) N e h 3N !i
i
e 2N
= (2E)N !N
N
Q
with ! N = i !i . The entropy is then equal to

S(E, V, N ) = kB log (E, V, N )

" #
X
= kB N log (2E) + 2N 2N log N + !i .
i

b)
Now we have
1 @S
=
T @E V,N
N
= kB
E

14
c)
First we calculate the partition function for 1 harmonic oscillator

Z
1 2 2 2
Zi = 3 dpdqe (p /(2m)+m!i q /2)
h
r s
2m 2
= h 3
m!i2
2 1
= .
! i h3
So the total partition function is equal to
N
2 N
ZN = ! .
h3

Finally we have
@ log ZN
E=
@
N
=

or E = N kB T .

15
2.4 Maxwell speed distribution
a)
We calculate as follows

* +
1
N
X pi
(v) = v
N m
i=1
N Z
1 X pi
= d v exp { H( )}
N N !h3N Z(N, V, T ) m
i=1
Z
1 p1
= d v exp { H( )} .
N !h3N Z(N, V, T ) m
Lets calculate that last integral, we see
Z Z ( !)
p1
N
mv2 X p2i
d v exp { H( )} = d exp +
m 2 2m
i=2
Z ( N
)
X p2i
mv2 /2
=e d exp .
2m
i=2

That last integral is very similar to the integral of the partition function, it
is simply the partition function divided by a gaussian integral. So we have
Z p1 N !h3N Z(N, V, T )m3/2 2
d v exp { H( )} = 3/2
e mv /2 .
m (2kB T )
So the velocity distribution is equal to
3
m 2
mv 2 /2
(v) = e .
2kB T

b)
The speed distribution is equal to
Z
g(v) = dv (|v| v) (v)
3 Z
m 2
mv 2 /2
= e dv.
2kB T |v|=v

16
That last integral is simply the surface area of a sphere in 3 dimension with
radius v. So we the speed distribution goes as follows

3
m 2
mv 2 /2
g(v) = 4v 2 e .
2kB T

The probability that kinetic energy

q lies somewhere
q between 0 and E we can
2E 2E 0
calculate as followed, where v = m and v 0 = m ,

Z E 3 Z v
0 0 m 2
E0
W (E )dE = 4 (v 0 )2 e dv 0
0 2kB T 0
3 Z E
p
m 2E
2
E0
= 3/2
e4 dE 0 .
2kB T 0 m
Z Ep
3 p
E0
= (2kB T ) 2 4 2 E0e dE 0 .
0

Dierentiating this equation with respect to E gives us

3p
W (E) = 2(kB T ) 2 Ee E .

c)
2
First we calculate
2 vx + vy2 , because of symmetry obviously vx2 = vy2 .
So we have vx + vy2 = 2 vx2 . Finally we see
3 Z
2 m 2
mv 2 /2
vx = dv vx2 e
2kB T
3 Z Z 2
m 2
mvx2 /2 mvy2 /2
= dvx vx2 e dvy e
2kB T
3 r
m 2 @
2 2 2
=
2kB T m@ m m
3 3/2
m 2 2 1 5/2
=
2kB T m m
1 kB T
= = .
m m

17

The probability that vx2 + vy2 > vx2 + vy2 is then
3 Z
m 2
mv 2 /2
P = dvx dvy dvz e
2kB T vx2 +vy2 >2/ m
Z
m m(vx2 +vy2 )/2
= e dvx dvy ,
2kB T vx2 +vy2 >2/ m
q
2
because the integral over vz is simply m . For the other integrals we
revert to polar coordinates
Z Z 2
m 2
P = p e mr /2 rdrd
2kB T r> 2/ m 0
+1
m 1 2
= e mr /2 q
kB T m 2
m
1
=e .

d)
The average kinetic energy we can calculate as follows

mv 2
hEi =
2
* +
m(vx2 + vy2 + vz2 )
=
2
3m 2
= vx
2
3kB T
= .
2
The probability that E > hEi is then
3 Z
m 2
mv 2 /2
P = 4 v2e dv
2kB T v 2 >3/ m
3 Z 3/2
m 2 2 u2
= 4 u2 e du,
2kB T u2 >3/2 m

18
 q
m
where we have substituted with u = 2 v. This gives us
Z 1
4 u2
P =p u2 e du
3/2
0, 21

2.5 Ideal gas in a gravitational field

a)
Denote with V the volume of the container. Lets call r the radius of the
cylinder. We calculate the partition function as follows

1
Z(N, V, T ) = (Z1 (V, T ))N
N!
Z Z N
1 p2 /(2m) mgqz
= dpe dqe
N !h3N
" Z #N
1 2m 3/2 2 b mgz
= r dze
N !h3N a
" #
1 2m 3/2 r2 N
= e mga e mgb
N !h3N mg

1 AN 1 mga mgb
N
= 3N N !
e e ,
T mg
h
where T = p
2mkB T
. The free energy is then

F (N, V, T ) = kB T log Z(N, V, T )

A mga mgb
= kB T N log N + N 3 log T + log + log e e 1 .
mg

With A = r2 and z = b a.

b)
The work being done is equal to

dW = Fa da + Fb db

19
where Fa is the force on the lower piston and Fb is the force on the upper
piston. So we have
@F
= Fa
@a
@F
= Fb
@b
So calculating this

mge mga N mge mga

Fa = N k b T mga mgb
= mga mgb
e e e e
N mge mgb
Fb = mga mgb
e e

c)
The hamiltonian remains unchanged when we interchange particles so hr ri i =
hr r1 i. Now we can calculate

(r) = N hr r1 i
Z Z N Z
Y Z
1 p21 /(2m) mgqz p2i /(2m) mgqi,z
= dp! e (r q1 )dq1 e dpi e dqi e
Z(N 1)!h3N
i=2
N 1
1 AN mgz 1 mga mgb
= 3N
e e e
Z(N 1)! T mg
N mge mgz
= mga mgb
e e
where z r = z. So
N mge mgz
p(z) = mga
A (e e mgb )
N mge mgz
= kB T
A (e mga e mgb )
(r)
= kB T
A
= kB T 0 (z)

20
2.6 Energy fluctuations in an ideal gas
Z
1
E 2
= H( )2 e H( ) d
N !h3N Z
Z
1 @2
= e H( ) d
N !h3N Z @ 2
@2Z
=Z 1 2.
@
@ log Z
We already know the identity hEi = @ , so we can conclude

@ 2 log Z @ 1 @Z
2
= Z
@ @ @
2
1 @2Z 1 @Z
=Z Z
@ 2 @

= E2 hEi2 .
@ log Z 3N
In the ideal gas we have E = @ = 2 . So we see

@ 2 log Z
Var(E) =
@ 2

@ 3N
=
@ 2
3N
= .
2 2
Var(E) 3N 4 2 2
Ultimately we have hEi2
= 2 2 9N 2
= 3N , which goes to zero as N ! +1.

21
2.7 Generalized equipartition theorem
Notice that for any i we have
@H
= sgn(pi,x )i s|pi,x |s 1 ,
@pi,x
@H
= sgn(qi,x ) i r|qi,x |r 1 ,
@qi,x

These relations give us

E = hHi
N X
X d
= hi | pi,x | s + i | qi,x |
r
i
i=1 x=1
XN X d
1 @H 1 @H
= pi,x + qi,x ,
s @pi,x r @qi,x
i=1 x=1

where the summation over x goes over each coordinate. The equipartition
theorem then gives us
d
N X
X
1 1
E= + kB T
s r
i=1 x=1

s+r
=N dkB T,
sr

The specific heat is then easily calculated as follows

s+r
cV = N dkB .
sr

Now the transformation i ! 32 i leaves the specific heat unchanged. For

the case of the three-dimensional harmonic oscillator we find E = 94 N kB T
and cV = 94 N kB .

22
2.8 Harmonic Oscillator in polar coordinates
a)
We calculate the one particle partition
function
as follows, with the polar
py
coordinates p = px2 + py , = bgtan px , r = x2 + y 2 and ' = bgtan xy ,
2 2 2 2

Z Z
4 2 1 p2
1 m !2 2
r
Z1 = 2 pe 2m dp re 2 dr
h 0 0
1 1
4 2 m p2 1 m !2 2
r
= 2 e 2m e 2
h 0 m !2 0
4 2
= 2 2 2
! h

b)
The kinetic energy is then
m 2
E= (x + y 2 )
2
m
= ((r cos r sin )2 + (r sin + r cos )2 )
2
m
= (r2 + r2 2 ).
2
So the conjugated momenta are

pr = mr,
p = mr2 .

The hamiltonian then becomes

1 m! 2 r2
H= (m2 r2 + m2 r2 2 ) +
2m ! 2
p 2 2 2
1 m! r
= p2r + 2 + .
2m r 2

c)
The one particle partition function is now given by

23
 Z Z Z p2
Z
1 p 2 m! 2 r 2 /2
Z1 = 2 e 2m dpr e
r dr e 2mr 2 dp d
h
r Z r
2 2m m! 2 r 2 /2 2m
= 2 re dr
h
" 2 2
# 1
4m 2 e m! r /2
= 2
h m! 2
0
4 2
= .
!2 2 h2

d)
e)
The partition function of N particles is now given by

Z1N
Z(N, V, T ) =
N!

1 2 2N
= .
N! ! h

We also find

2
log Z N N log N + 2N log
! h

So the internal energy is equal to

@ log Z
hEi =
@
2N
=

= 2N kB T.

The specific heat is then

@E
cV =
@T
= 2N kB

24
2.9 Diatomic molecules (1)
a)
Calculating the partition function for one diatomic molecule gives us

Z
1 K
|r1 r 2 |2
Z1 = 6 dr1 dr2 e 2

T Z
V K 2
r
= 6 dre 2 .
T

Where we used the substitution r = r1 r2 . We can approximate this

integral by simply integrating over entire R3 instead of just the volume V .
K 2
Since for large volumes V , the factor e 2 |r1 r2 | dies o exponentially fast,
this is a good approximation. We see
3/2
V 2
Z1 6 .
T K

The total partition function is then given by

3N/2
VN 2
Z(N, V, T ) =
N ! 6N
T K

The free energy is given by

1 3N 2
F = N + N log N + 6N log T N log V log .
2 K

b)
The specific heat is given by
@E
cv =
@T
@ 2 log Z @
=
@ 2 @T

@ 9N
2 1
=
@ kB T 2
9N kB
=
2

25
c)
Notice that
h i
Z p21 +p22 K
1 exp 2m + 2 |r1 r2 |2
h|r1 r2 |2 i = |r1 r2 |2 d
Z1 h3N
h i
Z exp p21 +p22 K
1 2 @ 2m + 2 |r1 r2 |2
= d
Z1 @K h3N
2 @ log Z1
=
@K
3
=
K

2.10 Diatomic molecules (2)

a)
We calculate the partition function as follows
Z Z N
1 |r12 r0 |
Z(N, V, T ) = dr1 dr2 e .
N !I 6N
T

When we take r2 to be constant to calculate the second integral, and de-

note with r = r1 r2 . The integral then becomes if we turn to spherical
coordinates

Z
|r12 r0 |
I= dr2 e
Z
|r r0 |
= dre
Z
|r r0 |
= drdd' cos r2 e

0
The term e |r r0 | will become small for large r, so we can approximate
the integral over the volume V with the integral over the entire volume.
Z r0 Z 1
2 (r r0 )
I = 4 r e + 4 r2 e (r0 r)
0 r0

The primitive of the functions we are integrating can be calculated using

integration by parts. The primitives of the first and second functions are
respectively

26

(r r0 ) r2 2r 2
e 2 2
+ 3 3 ,

2

(r0 r) r 2r 2
e + 2 2+ 3 3 .

So the integral simply becomes

r02 2r0 2 2e r0 r02 2r0 2
I = 4 2 2
+ 3 3 3 3
4 2 2 3 3

2
2r0 4 e r0
= 4 + 3 3

Finally we have for the partition function

(8V )N N
2 2 2 r0
Z(N, V, T ) = r0 +2 e
N !( )3N ( T )6N

The free energy is given by

log Z
F =
1
(N
N log N + 3N log( ) + 6N log( T )

+N log(8V ) + N log 2 2 r02 + 2 e r0 .

b)
The internal energy we can calculate by
@ log Z
E=
@
6N N 2 r02 + r0 e r0
= + 2 2 r 2 + 2 r0
.
0 e

27
The specific heat we then find as follows
@E
cV =
@T
@E
= kB
@(1/ )

@ @ 2 r02 + r0 e r0
= 6N kB + N kB 2 2 r 2 + 2 r0
@(1/ ) @ 0 e

2.11 Langevins theory of paramagnetism

Consider the Hamiltonian

N
X N
X
p2i
H( ) = B cos i
2m
i=1 i=1

of a system enclosed in a sphere of radius R. We use polar coordinates

so ri = ri (sin i cos 'i , sin i sin 'i , cos i ). Now calculating the partition
function we have
Z Z 2 Z
1 Y R 2
Z= r i dr i d' i sin i e B cos i di
N ! 3N
T i 0 0 0
Z N
1 (2R3 )N B cos
= sin e d .
N ! 3N
T 3N 0

Using the substitution u = cos we find

Z Z 1
sin e B cos d = e Bu
du
0 1
2 sinh( B)
= .
B
The partition function then becomes
N
1 4R3 sinh( B)
Z= 3N
N! T 3 B

1 V sinh( B) N
= 3N
.
N! T B

28
The induced magnetic moment we can calculate as follows
*N +
X
M= cos i
i=1
Z X
N PN Y
1
= 3N
cos i e B i=1 cos i
dri
ZN ! T i=1 i
Z PN
1 1 @ B i=1 cos i Y
= 3N
dri
ZN ! T @B
i
1 @ log Z
= .
@B
This we can calculate so
1 @[N log(sinh( B)) N log( B)]
M=
@B

N cosh( B) 1
=
sin( B) B

1
= N coth( B) .
B

b)
The magnetic susceptibility per atom is given by
1 @M
=
N @B
@ cosh( B) 1
= 2
@( B) sinh( B) B

sinh2 ( B) cosh2 ( B) 1
= 2 +
sinh2 ( B) ( B)2

1 1
= 2 2 2
( B) sinh ( B)

29
2.12 Van Leeuwens theorem
2.13 Stretching DNA
a)
Notice
Z YL
dbi F(rL r0 )
ZL = (|bi | b) e
4b2
i=1
Z YL Z
dbi F(rL r1 ) db1 F(r1 r0 )
= (|bi | b) e e
4b2 4b2
i=2
= ZL 1 Z1 .

So we have ZL = Z1L . We can calculate Z1 as follows

Z
db0 Fb0
Z1 = (|b0 | b)e
4b2

We revert to polar coordinates, where we choose the z-axis along F such

that F b0 = F b0 cos . So we see
Z Z Z 2
2 (|b0 | b) b0 F cos
Z1 = db0 b0 d sin e d'
4b2 0 0
Z
1
= d sin e bF cos
2 0
Z bF
1
= eu
2b F bF
1
= sinh( bF )
bF
1
= sinh f
f
where we used the substitution u = bF cos and have denoted with f the
product bF .

30
b)
Notice that
@e Fr @e F rx
=
@F @F
= rx e Fr

Now for the average extension of the chain along the x-direction, we see

X = hxL x0 i
Z YL
1 dbi
= (|bi | b) (xL x0 )e F(rL r0 )
ZL 4b2
i=1
Z Y L
1 dbi @ F(rL r0 )
= 2
(|bi | b) e
ZL 4b @F
i=1
1 @ log ZL
=
@F
@ log ZL
=b .
@f
The previous part of the exercise gives us

log ZL = L log(sinh f ) L log f.

So finally we have

L cosh f L
X=b
sinh f f

1
= Lb coth( bF )
bF

31
c)
Expanding X in terms of f we find
!
f2
1+ 2 + ... 1
X = Lb 2
f (1 + f6 + . . .) f

Lb 1 + f 2 /2
1
f 1 + f 2 /6
!
Lb f2
f2
f 3(1 + 6 )
!
f
Lb f2
3(1 + 6 )
Lb
f
3
Lb2 F
,
3
where we made the approximations cosh(f ) 1 + f 2 /2, sinh f = 1 + f 2 /6
and 1 + f 2 /6 1. Ultimately we have F 3kLb
BT X
2 .

d)
We know

ef + e f 1
X = Lb f f
e e f

1 2
= Lb 1
f 1 e2f
1
At high forces, f too wil be large so we can approximate 1 e2f
0 and so

1
X Lb 1
f
kB T 1 1
This gives us F = b Lb X which is not in agreement with experiment.
1
Im not entirely sure about the last section of this exercise, anyone willing to confirm?

32
2.14 Stretching a polymer: the low force limit
We recalculate the partition function
Z Y
L
H(b1 ,b2 ,...,bL ) F(rL r0 )
ZL = dbi e e .
i=1

Denote with ZL0 the partition function of the system in absence of the force
Z Y
L
ZL0 = dbi e H(b1 ,b2 ,...,bL )
,
i=1

and denote with X 0 end to end distance in absence of the force, so

Z Y
L
1
X0 = dbi (xL x0 )e H(b1 ,b2 ,...,bL )
ZL0
i=1

Approximating the second exponential by e F(rL r0 ) 1 + F (rL r0 ).

We find that
Z YL
ZL dbi e H(b1 ,b2 ,...,bL ) (1 + F (rL r0 ))
i=1
Z Y
L
!
F
ZL0 1+ 0 dbi e H(b1 ,b2 ,...,bL )
(xL x0 )
ZL
i=1
ZL0 1 + F X 0
1 @ log ZL
In the previous exercise we proved that X = @F so we find2

1 @
X log ZL0 + log(1 + F X 0 )
@F
1 X0
.
1 + F X0

2.15 Worm like chain

3

2
Obviously this is false, I would be very grateful to anyone who can show me a more
correct method.
3
Working on this

33
a)
Consider the unit vectors ti and ti+l in polar coordinates

ti = cos z + sin sin 'y + sin cos 'x

ti+l = cos 0 z + sin 0 sin '0 y + sin 0 cos '0 x

2.16 Stretching a gaussian polymer

If we write ri = Ri Ri 1, we see
Z Y PL PL
K 2
ZL = dri e i=1 ri + F i=1 ri .
i

This we can factorize as follows

Y Z
Kr2i + Fri
ZL = dri e
i
Y
= Z1
i
= (Z1 )L
Pm
Now notice that Rm+n Rn = i=1 rn+i . Since the partition function
factorizes, we have hri rj i = hri ihrj i when i 6= j. All of this gives us

* !2 +
D E m
X
2
(Rm+n Rn ) = rn+i
i=1
* m
! 0 m
1+
X X
= rn+i @ rn+j A
i=1 j=1
m X
X m
= hrn+i rn+j i
i=1 j=1
m
X m
X

= r2n+i + hrn+i i hrn+j i .
i=j i6=j

We find that because we can interchange

all of the vectors ri in the hamil-
tonian that hri i = hrL i and r2i = r2L . So we have

34
 D E
(Rm+n Rn )2 = m r2L + m(m 1) hrL i2

because if i and j vary from 1 to m there are m ways for i to be equal to j

and m(m 1) ways to be dierent from each other.

Z Y PL PL
1 K 2
i=1 ri + F i=1 ri
hrL i = dri rL e .
ZL
i
Z Z LY1 PL PL
1 Kr2L + FrL K 2
i=1 ri + F i=1 ri
= drL e rL dri e .
ZL
i=1
Z
ZL 1 Kr2L + FrL
= drL e rL .
ZL

ZL 1 Z1L 1 1
We have proven before that ZL = Z1L
= Z1 . Now if we write F =
(Fx , Fy , Fz ) and ri = (xi , yi , zi ) we see

Z
1 2
hxi i = drL xL e KrL + FrL
Z1
Z
1 @ 2
= drL e KrL + FrL
Z1 @Fx
1 @Z1
=
Z1 @Fx
1 @ log Z1
= .
@Fx

In an analogous way we can prove that hr2L i = 1 @ log Z1

@K . Now all that is
left is to calculate Z1 ; if we identify x with 1, y with 2 and z with 3 we see

Z
Kr2 + Fr
Z1 = dre
3 Z
Y
K2 + F
= de
=1

R ax2 +bx
p b2
The gaussian integral is equal to dxe = ae
4a for any a > 0 and

35
b 2 R. So we have

Y3 r
42 FK2
Z1 = e
K
=1

3/2 2
= e 4K F .
K

Finally we see

3
X
2
hrL i = hi2
=1
3
1 X @ log Z1 2
= 2
@F
=1
0 12
3 3 F2
1 X @@ 2 log( K) + 4K
A
= 2
@F
=1
3
1 X 2F 2

= 2 4K 2
=1
F2
=
4K 2
and

1 @ log Z1
r2L =
@K

3 F2
1@ 2 log( K) + 4K
=
@K
3 F 2
= +
2 K 4K 2
3
= + hrL i2 a2 .
2 K

Ultimately we find that 4

4
Obviously this answer diers from that in the text, anyone spotting my mistake?

36
 D E
(Rm+n Rn )2 = m r2L + m(m 1) hrL i2
F2
= ma2 + m(m 1)
4K 2

Fa 2
= ma2 + m(m 1)a 2
3kB T

2.17 Rigid monomeric chain

The hamiltonian is given by
N
X
H= (i F li ).
i=1

N
Now because there are to choose i particles (with energy and length
i
a) out of N particles we find for the partition function
X PN
Z= e i=1 (i F li )

s
X
N
N

= exp ( [i + (N i) ] + F [ia + (N i)b])
i
i=0
N
X
N ( F b) N
=e [exp ( ( ) + F (a b))]i
i
i=0
N
N ( F b) ( )+ F (a b)
=e 1+e
N
+ Fb + F a
= e +e .

37
The mean length of the chain molecule is then
*N +
X
L= li
i=1
N
1 XX PN
i=1 (i F li )
= li e
Z s
i=1
1 1 @ X PN
i=1 (i F li )
= e
Z @F s
1 @ log Z
=
@F
N be + F b + ae + F a
=
e + F b + e + F a
be + F b + ae + F a
=N .
e + F b + e + F a

2.18 Solid-Gas equilibrium

a)
The hamiltonian of the particles in solid phase is that of Ns independent
harmonic oscillators
Ns
X Ns
X
p2i m! 2 r2i
Hs ( ) = + .
2m 2
i=1 i=1

Now the partition function of this system is

Z Z N s
1 p2 m! 2 r2
Zs (T, V, Ns ) = e 2m dp e 2 dr
Ns !h3Ns
3Ns /2
1 4 2
=
Ns !h3Ns 2!2
3Ns
1 2
= .
Ns ! !h

The hamiltonian of the particles in gas phase are

Ng
X p2i
Hg ( ) = + Ng .
2m
i=1

38
Now the partition function of this system is
Z Z Ng
1 p2
Zg (T, V, Ng ) = e 2m dp dre
Ng !h3Ng
3Ng /2
V Ng e Ng 2m
=
Ng !h3Ng

b)
The total free energy is then given by
1
F (T, V, N, Ng ) = (log Zs (T, V, N Ng ) + log Zg (T, V, Ng ))

1 2
= (N Ng ) log(N Ng ) + (N Ng ) + 3(N Ng ) log
!h

3Ng 2m
Ng + Ng log V Ng log Ng + Ng + log
2 h2
(N Ng ) log(N Ng ) + Ng log Ng + N + 3(N Ng ) !h
= log
2
Ng 3Ng h2
+ Ng log V + log .
2 2m
@F
There is only equilibrium when @Ng = 0 so there is equilibrium when

@F
0=
@Ng
!h 3 h2
= log(N Ng ) + log Ng 3 log + log V + log
2 2 2m
holds. This is equivalent to
3 3/2
N 2 h2
1 =
Ng !h 2m
3/2
1 2
= e .
V m !2

39
That gives us
3/2 3
Zg (T, V, 1) Ve 2m 2
=
Zs (T, V, 1) h3 !h
3/2
!2
=Ve
2
Ng
=
N Ng

c)

@F
P =
@V
Ng kB T
=
V

2.19 Ideal gas in grand canonical ensemble

a)
Remember that the partition function of the ideal gas is

VN
Z(N, V, T ) = .
N ! 3N
T

So we know that
X
N
(, V, T ) = e Z(N, V, T )
N
X VN
N
= e
N
N ! 3N
T
X 1 V e N

= 3
N! T
N


Ve
= exp 3
T

40
b)
The distribution of the total number of particles is

e N Z(N, V, T )
P (N ) =
(, V, T )

Ve N VN
= exp 3 e
T N ! 3N
T
hN iN
= exp ( hN i)
N!
Ve
with hN i = 3 .
T

c)
Now we see
X 2
N2 = N P (N )
N
X hN iN
2
= N exp ( hN i)
N!
N
X @N 1
hN i
=e hN i N
@ hN i N !
N
!
@ X hN iN
= e hN i hN i ehN i N e hN i .
@ hN i N!
N

P hN i hN i
N P
Now the expression N N e N! = N N P (N ) is the mean number of
particles hN i so we have
hN i @ h hN i i
N2 = e hN i e hN i
@ hN i
= hN i2 + hN i .

Ultimately this gives us

N2 hN i2 = hN i .

41
2.20 Coexisting phases
a)

N
There are ways to choose i particles (in the solution) out of N particles.
i
So the partition function is

N
X
1 N
Z= 3N N !
V1i V2N i ei

T
i
i=0
1 N

= 3N N !
V1 e + V2 ,
T

h
where T = p
2mkB T
.

b)
The average number of particles in solution is given by
N
X
1 N
hN1 i = 3N N !
iV1i V2N i ei
Z T
i
i=0
N
V1 @ X N
= V1i V2N i ei
Z 3N
T N ! @V1 i=0 i
@ log Z
= V1
@V1
@ log(V1 e + V2 )
= N V1
@V1
V1 e
=N .
V1 e + V2
The average number of particles in gas phase is then

hN2 i = N hN1 i
V2
=N .
V1 e + V2

c)
The grand canonical partition functions are given by

42
 X V N eN e 1 N
1
1 (V1 , T, 1 ) = 3N N !
N T
!N
X 1 e (+1 )
= V1 3
N! T
N
!
V1 e (+1 )
= exp 3
T

and
2

V2 e
2 (V2 , T, 2 ) = exp 3 .
T
Now the average number of particles in solution are given by
1 X V N eN e 1 N
hN1 i = N 1 3N
1 (V1 , T, 1 ) T N!
N
1 1 @ X V1N eN e 1 N
= 3N N !
1 (V1 , T, 1 ) @1 T N
1 @ log 1 (V1 , T, 1 )
=
@1
V1 e (+ 1)
= 3 .
T
In the same way we find
1 @ log 2 (V2 , T, 2 )
hN2 i =
@2
V2 e 2
= 3 .
T
Now imposing that these are equal to those computed in b) we have
V1 e V1 e (+1 )
N
= 3 ,
V1 e + V2 T
V2 V2 e 2
N
= 3 .
V1 e + V2 T
Dividing the left side of one equation by the left side of the other we find
(1 2 )
1=e ,
so we must have 1 = 2 .

43
2.21 Arrhenius law

44
3 Interacting Systems
3.1 Hard Rods
The momentum part of the integral can easily be calculated so we see
Z Y
1
ZN = N
(x1 , . . . , xN ) dxi ,
N! T i
p
where T = ph2m .
We order the particles from left to right, such that x1 is outermost left, x2
right from x1 and so forth with xN outermost right. This ordering isnt
arbitrary, the positions of the particles may as well be interchanged. So we
introduce a factor N ! to correct this

Z L /2 Z L /2 Z L /2 Y
1
ZN = N
dx1 dx2 . . . dxN Ai 1,i
T /2 /2 i

where we have introduced Ai 1,i which is zero when |xi xi 1 | < and
equal to one when |xi xi 1 | . Now the first particle has to leave room
for N 1 other particles, this means that its upper bound is L N + /2.
The k-th particle has to leave room for N k other particles so its upper
bound is L (N k + 1) + /2. The k-th particle has to have a distance
larger than from the (k-1)-th particle so its lower bound is xk 1 + . We
see

Z L N + /2 Z L (N k 1/2) + /2 Z L /2
1
ZN = N
dx1 . . . dxk+1 . . . dxN
T /2 xk + xN 1+

Using the change of variable yk+1 = xk+1 (k + 1/2) we see

Z L N Z L N Z L N
1
ZN = N
dy1 dy2 . . . dyN
T 0 y1 yN 1
Z L N
1 (L N x)N 1
= N
T 0 (N 1)!
(L N )N
= NN!
.
T

45
First we calculate the internal energy as follows
@ log ZN
E=
@
@ log T
=N
@
N
=
2
N kB T
=
2
N kb
so we have for the specific heat cL = 2 .

b)
The pressure is now given by

@F
p=
@L
L N
1 @(N log T
N log N + N )
=
@L
1
=
(L N )
kB T
=
L N

3.2 Hard Disks

a)
The first disk that is placed in the area has the total area of S available, if
we neglect the area that is lost at the boundary. The second disk has again
an area of S available minus the area of a circle of radius . So the eective
area available is A2 = S 2 2 S.

b)
Using the same approximation as before, we try to find the approximate area
AN available for N particles. Let us put the particles in S in a particular
order. Then for the first particle theres an area of S available, the second

46
has S Q 2 , the third S 2 2 and so forth. Multiplying this we get
aN = N i=0 (S i 2 ). Notice we have the following recursion relation

aN = SaN 1 N 2 aN 1

2 S
= aN 1 N .
2
To which the solution is
2 )N S
( N +1 2
aN = S
.
1 2

Now because we placed the particles in a particular order, we have to intro-

duce a factor of N ! to account for all the orders the particles might come
in. So An = N !an . The momentum part of the partition function is easily
N
integrated, it is simply 2m
h 2 . So the total partition function is
N
1 2m
Zn = An
N! h2
2 )N S N
( N +1 2 h2
= S
1 2
2m

The approximation is good for small . Then the area lost at the boundary
will be negligible.

c)
Now if we take AN to be the exact available area. Now because An doesnt
depend on we see
@ log ZN
E=
@
@ log
=N
@
N
=

= N kB T

so the specific heat is cV = N kB . This result is exact, since we didnt

approximate AN here.

47
3.3 Virial expansion for Hard Spheres
a)
We know

0 |q| 0
f (q) =
1 |q| < 0

so f (q) = g(q) 1.
The second virial coefficient we calculate as follows
Z
1
b2 (T ) = dqf (q)
2
Z
1
= dq
2 S(0, 0 )
2 03
= ,
3
where we used S(0, 0) to denote a sphere with radius 0 and center 0.

b)
The third virial coefficient we calculate as follows

Z Z
1
b3 (T ) = dq1 dq2 f (q1 )f (q2 )f (q12 )
3
Z Z
1
= dq1 dq2 f (q12 ).
3 S(0, 0 ) S(0, 0 )

First fix some q1 , and we calculate the following integral

Z Z
dq2 f (q12 ) = dq2 .
S(0, 0) S(0, 0 )\S(q1 , 0 )

Notice that this is precisely the volume in the intersection between a sphere
with center 0 and radius 0 and a sphere with center q1 and radius 0 . This
volume is also equal to the volume of a spherical cap of the first sphere plus
the volume of a spherical cap of the second sphere. So first we will figure
out the volume of a spherical cap.

48
 Figure 1: The parts in blue and red are both spherical caps.

A spherical cap is a portion of the sphere cut o by a plane. The volume of

the spherical cap is given by 5

h2 (3r h)
Vcap = .
3
For the first sphere take h as described in figure 1 to be h1 and for the
second h2 . By symmetry h1 must be equal to h2 and h = 0 |q21 | . Now
the volume of the two spherical caps is given by
2
Vcap = h (3 0 h1 ) + h22 (3 0 h2 )
3 1
2(2 0 |q1 |)2 |q1 |
= (2 0 + )
12 2
(2 0 |q1 |)2
= (4 0 + |q1 |).
12
Finally we can calculate the third virial coefficient as follows
Z
1 (2 0 |q1 |)2
b3 (T ) = dq1 (4 0 + |q1 |)
3 S(0, 0 ) 12
5
You can see this by taken the volume of the spherical wedge described by and
subtracting the volume of the cone with the circle with radius a as base.

49
Switching to spherical coordinates we find
Z 0
4 2
b3 (T ) = r2 (2 0 r)2 (4 0 + r)dr
3 12 0
2 5 06
=
9 2
2
5 2 03
=
8 3
5
= b2 (T )2
8

3.4 Second virial coefficient and the Boyle temperature

a)
We see that
8
< 1 0<r<
(r)
e 1= e 1 <r<2
:
0 r>2
The second virial coefficient is equal to
Z +1
b2 (T ) = 2 drr2 e (r)
1
0Z Z 2
2 2
= 2 ( r )dr + e 1 r dr
0
Z 2 Z 2
2 2
= 2 r dr e r dr
0
2
= 8 3 e (8 3 3
)
3
2 3 14 3
= + 1 e .
3 3
Here the first term is due to the hard sphere potential and the second term
due to the attractive part of the potential.

b)
Denote with Tb the Boyle temperature. So we have
0 = b2 (Tb )
16 3 14 3
= e k B Tb .
3 3

50
This gives us
8
e k B Tb = .
7

So the Boyle temperature is Tb = kB log(8/7) . Considering that b2 (T ) is an
increasing function we have that b2 (T ) is positive for T > Tb and negative
for b2 (T ) for T < Tb .

3.5 Virial coefficient

The second virial coefficient is given by
Z +1
b2 (T ) = 2 drr2 e (r)
1
0
Z +1
2 3
= 2 dr e r6 1 r2 .
3

Expanding the exponential we find

3 1 Z
X +1 n
2 2
b2 (T ) = 2 drr
3 r6
n=1
3 Z +1
2 1
2 dr
3 r4
2 3 2
3
.
3 3
So we have

an
P = nkB T 1 + bn
kB T
3
where b = 23 and a = 323 which looks like the low desnity expansion of
the van der Waals equation.

3.6 Second virial coefficient of Argon

a)
We calculate the second virial coefficient for the potential (r).

51
 Z 1
(r)
b2 (T ) = 2 dr e 1 r2
0
Z Z !
0
= 2 drr2 + e
1 r2 dr
0

2 3 2( 03 3)

= e 1 .
3 3
Expanding e 1 we find

2 3 2( 03 3)
2 2
b2 (T ) +
3 3
2 3 2( 03 3) 1 22 ( 03 3) 1
2 .
3 3kB T 3kB T2

So we find
2 3
A=
3
2( 03 3)
B=
3kB
22 ( 03 3)
C= 2 .
3kB

Inverting these relations we find

3A 1/3
=
2
1/3
0 3 2
= (A + B /C)
2
C
= kB .
B

b)
3.8.12 is simply a quadratic equation in 1/T so we find
p
1 B + B 2 + 4AC
= .
Tb 2A

52
We only consider the positive solutions, because we cant have any negative
temperatures (in Kelvin that is). So for the Boyle temperatur we find

2A
Tb = p .
B+ B 2 + 4AC

3.7 The Flory exponent of a polymer

Dierentiating the expression 3.8.14 with respect to V gives kB T n
kB T b2 n2 which corresponds precisely to the virial expansion.
Now we can find the minimum of F given by 3.8.15 as follows

@F
0=
@R
3R b2 N 2
= kB T d d+1 .
N a2 R

This equation is satisfied for

db2 a2 3
Rd+2 = N ,
3
3
and so R N d+2 .

3.8 The mean field theory of non-ideal gases

a)
Calculating the partition function for the system described by H0 we see
N
Z0 = e ZI

VN
where ZI is the partition function of the ideal gas which is ZI = N ! 3N
. So
T
the free energy of this system is
log Z0
F0 ( ) =
N log V + N N log N + 3N log T
=N + .

53
We also see that
0 1
Z X
1 (K( )+N ) @
hH1 ( )i0 = d e (|ri rj |) N A
N !h3N Z0
i<j
N 1 Z
N (N 1)V N
= e dr (|r|) N
2N !Z0 3N
T
N (N 1)
= a N
V
N2
a N
V
R
where a = 12 dr (|r|).
Now we see that
N log V + N N log N + 3N log T
F( ) = f racN 2 V a + ,

which is already minimal so

N2 N log V + N N log N + 3N log T

Fe = a+ .
V

b)
From this we find the following equation of state

@ Fe
P =
@V

N2
@ V a + N kB T log V
=
@V
N kB T aN 2
= .
V V2
This method cannot
R work if the pair potential is slowly decaying because
then the integral dr (|r|) diverges. It also can not contain a hard repulsive
core, because then (r) diverges at zero, making the integral diverge too.

54
3.9 The critical exponents of a van der Waals fluid
3.10 One dimensional Ising model
a)
The partition function is given by
X X PN PN
h i=1 si + J i=1 si si+1
Z= ... e
s1 =1 sN =1

X N
X Y
hsi + Jsi si+1
= ... e
s1 =1 sN =1 i=1

X N
X Y
= ... Tsi ,si+1
s1 =1 sN =1 i=1

with
J h J h

e e
T = J+ h J+ h .
e e

Now notice that

X X
Z= ... Ts1 ,s2 Ts2 ,s3 . . . TsN ,s1
s1 =1 sN =1
X
N
= (T )s1 ,s1
s1 =1
N
= Tr(T ).

Now the trace of a matrix is equal to the sum of its eigenvalues. If are
the eigenvalues of T then N
are the eigenvalues of T
N so we have

N N
Z= + + .

The eigenvalues satisfy the characteristic equation

e J h e J+ h e 2 J = 0.

This is equivalent to
2 J
2e cosh( h) + 2 sinh( J) = 0,

which has the following solution

55
 q
J
=e cosh( h) e2 J cosh2 ( h) 2 sinh( J)
r
J e2 J
=e cosh( h) (1 + e2 h +e 2 h) e J +e J.
4

3.11 The Infinite-range Ising-model

a)
Calculating the partition function using 3.8.28 we find

0 !2 1
X X
Z=e /2
exp @ si A
2N
{si } i
r !
e /2 XZ 1 2 X
= p dy exp y + si y .
2 2 N
{si } i

Switching the sum and the integral and using the fact that
r !
X X X Y q s
exp si = e N i
N
{si } i {si } i
!N
X q s
= e N
s=1
" r !#N

= 2 cosh ,
N

we see that

Z " r !#N
e /2 1 2
y
Z= p dye 2 2 cosh
2 N
" r !#N
/2
=e 2 cosh
N

56
b)
Now the free energy is given by
r !!

F = N kB T log 2 cosh .
2 N

3.12 The mean field solution of the Ising model

57
4 Quantum Statistical Mechanics
4.1 Quantum Harmonic Oscillators
a)
The classical partition function, as calculated in 2.3, is given by

2 N
Z(N, V, T ) = .
! h3
Now the internal energy is given by
@ log Z
E=
@
= N kB T,
and the specific heat
cV = N kB .

b)
1
The energy of a quantum harmonic oscillator is given by n = ~! n + 2 .
So the quantum partition function can be calculated as follows

X N
X !
1
Z(N, V, T ) = exp ~! ni +
2
{ni } i=1
1
!N
~! X
~!n
= e 2 e
n=0
~!
!N
e 2
= ~!
1 e
N
~!
= 2 sinh .
2
Now the internal energy is given by
@ log Z
E=
@

N ~! ~!
= coth ,
2 2

58
and the specific heat by
@E
cV =
@T
~2 ! 2 1
= 2
.
4kB T sinh2 ~!
2kB T

Now expanding for example the expression for E we find

2 ~2 ! 2
1+ 8 + ...
E = N ~! ~! 3 ~3 ! 3
2 + 86 + ...
2 ~2 ! 2
1+ 8 + ...
= N kB T 2 ~2 ! 2 .
1+ 24 + ...
~!
Now for temperatures such that << 1 or T >> k~!
kB T B
, the energy reduces
to E = N kB T which is the classical energy for the harmonic oscillator.

4.2 Low temperature limit of a quantum partition function

The internal energy is given by
@ log Z
E=
@
e E 1 E + E e E
1 2
=
e E1 (1 + e E)

E1 + (E1 + E)e E
= E
.
1+e
The specific heat is then given by
@E
cV =
@T
1 @E
=
kB T 2 @
E(E1 + E)e E 1+e E + E1 + (E1 + E)e E Ee E
1
=
kB T 2
(1 + e E )2
2
1 E2e E E 2 E
= = cosh .
kB T 2 (1 + e E )2 kB T 2 2

E E
E E2
At low temperatures 1 + e 1 so cV = kB T 2
e kB T
e kB T
.

59
4.3 Ideal gas with internal degrees of freedom
i)
The kinetic energy of a particle enclosed in a volume V = L3 is given by

h2
Ekin = (n2 + n2y + n2z ),
2mL2 x
where nx , ny and nz are integers. The quantum partition function is then
given by
N
!
X h2 X 2 2 2
Z(N, V, T ) = exp (nx,i + ny,i + nz,i )
2mL2
{(ni,x ,ni,y ,ni,z )} i=1
1
X !3N
h2 2
= exp n
n= 1
2mL2
Z 1 3N
h2 2
L exp x dx
1 2m
p !3N
2m
= L p
h

where we have approximated the sum by an integral. Now the energy is

equal to
@ log Z
E=
@
3N
= kB T,
2
3N
and the heat capacity cV = 2 kB .

60
ii)
The partition function for molecules with vibrational degrees of freedom is
given by
X PN
Z= e ~! i=1 (ni +1/2)
{ni }
1
!N
X
~!/2 ~!n
= e e
n=0
N
1
~!/2
= e
1 e ~!
N
~!
= 2 sinh .
2

The energy is now given by

~! ~!
E= coth ,
2 2

and the specific heat

@E
cV =
@T
~2 ! 2 1
= 2
.
4kB T sinh2 ~!
2kB T

As calculated in 4.1. Now the heat capacity at low temperatures goes to

zero and for high temperatures reduces to

lim cV = N kB .
!0

4.4 When are quantum eects important?

4.5 Bose-Einstein, Fermi-Dirac and Maxwell-Boltzmann statis-
tics
If the particles obey Bose-Einstein statistics or Maxwell-Boltzmann6 statis-
tics, all nine configurations are permitted, that is particle 1 can take on any
6
This isnt mentioned in the course notes but section 7.5 in the book by Sethna deals
with this.

61
value of 0, or 2 and so can particle 2. If the particles obey Fermi-Dirac
statistics, only six configurations are permitted, that is where the energy
level of particle 1 and particle 2 dier.

The partition functions are

2
ZBE = 1 + e + e 2

1+e +e 2 2
ZM B =
2!
2
2 2 4 2 3
ZF D = 1 + e +e 1 e e = 2e + 2e + 2e .

The internal energies are then given by

1 + 2e

EM B = EBE = 2e
1+e +e 2

1 + 2e
EF D = + e .
1+e +e 2
For T ! 0, ! 1 and so EM B = EBE ! 0 but EF D ! . For T ! 1,
! 0 and so EM B = EBE ! 2 and EF D ! 2.

4.6 Quantum Corrections in a Bose ideal gas

We write
X 1
P
= an xn ,
nkB T
n=0

where x = n 3. According to 4.2.12 and 4.2.13 we have

T
1
X X1
n+1 zl
an x = ,
n=0 l=1
l5/2
X1
zl
x= .
l=1
l3/2

Filling in the second equation into the first, and working out for the first
few orders of z we find

1 1 1 1 1
za0 + z a0 p + a1 + z a0 p + a1 p + a2 = z + z 2 p + z 3 p + . . .
2 3
2 2 3 3 2 4 2 9 3

62
Since equal power series must have equal coefficients, we have

a0 = 1,
1 1
a0 p + a1 = p ,
2 2 4 2
1 1 1
a0 p + a1 p + a2 = p .
3 3 2 9 3
1 1 p1 2 .
Now these equations have the solutions a0 = 1, a1 = p
4 2
and a2 = 8 39
7

4.7 Bose-Einstein condensation in two dimensions?

The quantum partition function is given by
X
p2 /(2m)
log = log 1 e .
p

Now using 4.2.9 and z = e we have

1
XX zl p2 l/(2m)
log = e
p
l
l=1
Z 1
X
A zl p2 l/(2m)
dp e
h2 l
l=1
1
X
A zl
= 2 2
.
T l=1 l

where the sum over p is replace by an integral. Now we also find

X
N= hnp i
p
z X z
= + p2 /(2m)
.
1 z e z
p6=0

7
In the notes theres a dierent answer, but I fed this into maple, and it gave the same
answer as my solution. If you find another solution that corresponds to the one in the
notes or an error in this solution, please let me know.

63
Now integrating gives
2 1
X
T z zl
N= +
A 1 z l
l=1
2
T z
= log(1 z).
A 1 z

4.8 Bose condensation in a band

UNDER CONSTRUCTION (any solutions you have for the following exer-
cises, Ill happily receive)

4.9 Bose-Einstein condensation in a harmonic potential

The energy levels are given by (nx , ny ) = ~!(nx + ny + 1). For any given

energy , the area described by nx + ny < ~! 1 is a triangle in the nx , ny
1 2
plane with area N () = 2 ~! 1 .
Now the density of states is given by g() = dNd() = ~2 !~!2 . Given a chemical
potential , the amount of particles in the system is equal to
Z 1
g()
N () = ( )
dx.
0 e 1
The maximal value is
Z 1
1 (x ~!)
Nmax = 2 2 dx
~ ! 0 e x 1
1 1 2
= 2 2 2 .
~ ! 6
So the amount of particles in this approximation is bounded, if there are
more particles in the system than this maximum value the system becomes
a Bose-Einstein condensate.
In one dimension the energy is given by (n) = ~! n + 12 , so the density
1
of states is given by g1D () = ~! . Now the amount of particles,
Z 1
1 dx
N () =
~! 0 e (x ) 1

isnt bounded, so Bose-Einstein condensation does not occur.

64
4.10 Photons and phonons are bosons
A quantum harmonic oscillator with frequency ! has the energy = ~! n + 12 ,
shifting the zero of this energy, gives = ~!n. The canonical partition func-
tion for a quantum harmonic oscillator of frequency ! is then
1
X
~!n
Z= e
n=0
1
=
1 e ~!
The grand canonical partition function for bosons filling a single state with
energy ~! is
1
() = .
1 e ( ~!)
Now we see that (0) = Z.

4.11 Black body radiation

a)
We know that k = L (nx , ny , nz ) where nx , ny and nz are positive integers.
3
Now the amount of photons in a volume element dk is 2 L3 dk. Now the
number of oscillators in [!, ! + d!] is
1 L3 V
2 3 4k 2 dk = 2 3 ! 2 d! = g(!)d!.
8 c

b)
The grand canonical partition function is now given by
Z 1
log = d!g(!) log 1 e ( ~!)
0
Z 1
V
= 2 3 d!! 2 log 1 e ( ~!) .
c 0

c)
The pressure of the gas is given by
P V = kB T log
Z
kB T V 1 ~!)
= 2 3 d!! 2 log 1 e .
c 0

65
Using integration by parts, we find
Z
V 1 1 1
PV = 2 3 d!~! 3 ~!
c 3 0 e 1
E
= .
3

d)
The average energy of the system is now given by
Z 1
~!
E= d!g(!) ~!
0 e 1
Z 1
V 1 x3
= 2 3 4 3 dx x
c ~ 0 e 1
4
V kB T 4
= .
15~3 c3

e)
Notice that
Z 1
~!
E= d!g(!) ~!
0 e 1
Z 1
=V d!u(T, !),
0

such that
g(!) ~!
u(T, !) =
V e ~! 1
~! 3
= 2 3 .
c (e ~! 1)

f)
Now for ~! << 1 we have e ~! 1 ~! such that

!2
u(T, !) = kB T.
2 c3

66
4.12 Phonons on a String
a)
4.13 Debye Model
4.14 Ideal Fermi gas in two dimensions
4.15 Landau Theory of diamagnetism
4.16 Pauli spin paramagnetism
a)
The magnetization is equal to
X 1 p2

pi ,si
M= pi ,si e
B 2m
{pi ,si }
D 2E
p
E 2m
= .
B

4.17 Particles in magnetic field

The canonical partition function is given by
X PN
Z= e H i=1 si
{si }
!N
X
Hs
= e
s=1

= (2 cosh( H))N .

Now the internal energy is given by

@ log Z
E=
@
= N H tanh( H).

And the entropy is given by

E F
S=
T
H
= N (kB log(2 cosh( H)) tanh( H))
T

67
The specific heat is given by

N @ tanh( H)
cV =
kB T 2 @
N H
= .
kB T 2 cosh( H)2

The total magnetization is given by

* N
+
X
M= si
i=1
E
= .
H
Finally the magnetic susceptibility is
@M
=
@H
@ sinh( H)
= N
@H H cosh( H)

@ sinh( )
= N 2 with = H
@ cosh( )
sinh( )
= N 2 .
cosh( )2

4.18 High temperature specific heat of metals: a paradox?

4.19 Electronic contribution of specific heat
4.20 White dwarfs

68