STATISTICAL PHYSICS

Phonons; Virial Expansion Tutorial Sheet 4

The questions that follow on this and succeeding sheets are an integral part of this course. The

code beside each question has the following significance:

• K: key question – explores core material

• R: review question – an invitation to consolidate

• C: challenge question – going beyond the basic framework of the course

• S: standard question – general fitness training!

4.1 Debye Model with a di↵erent density of states [S]

Consider a 3d solid consisting of N atoms where the density of modes is

g(!) = b! 4

where b is a constant. The frequencies range from zero to some cut-o↵ !max .

Find an expression for !max .

Use !max to define a characteristic temperature and identify high T and low T regimes

Calculate the total energy E and the heat capacity in the low and high temperature limits,
which you should define. Express your results purely in terms of N, h, k, T and b (and a

dimensionless integral where required).

4.2 High and low temperature limits and corrections to Debye model [s/c]

For the Debye model of phonons in a d-dimensional isotropic solid containing N atoms,

a) Show that
N d2 h̄!D

E= f (↵)

↵(1+d)
h̄!D

where ↵ = and

kT Z ↵
xd

f (↵) = dx .
0 ex 1

b) In the high temperature limit kT h̄!D calculate the leading behaviour of CV and

first correction to this behaviour.

c) Show that

f (1) = ⇣(d + 1) (d + 1)

where the Riemann zeta function is defined as

1
X 1

⇣(s) = s

n=1 n

and the Gamma function is defined by

Z 1

(z) = uz 1 e u
du
0

d) By expressing f (↵) = f (1) f (↵), calculate the leading behaviour of, and first

correction to, CV .

4.3 Second Virial Coefficient [S]

Show that for a spherically symmetric potential (r), the expression for the second virial

coefficient may be written as

Z h i

B2 = 2⇡ r2 1 e (r)/kT
dr .

If a gas of interacting particles is modelled as hard spheres of radius a/2, show that the

second virial coefficient takes the form:

2⇡a3

B2 = .
3

4.4 Simple form Second Virial Coefficient [S]

Assuming that (r) is large (on the scale of kT ) and positive for r < r0 and small for

r > r0 , show that the second virial coefficient may be written as

a0
B2 (T ) = b0

kT

where you should obtain expressions for a0 and b0 .

Compare this form of B2 with that implied by the Van der Waals equation of state.

Calculate the entropy and show that

S = SIdeal N kb0 ⇢

Comment on why the entropy is reduced from the standpoint of information theory.

4.5 Failure of Perturbation Theory for Coulomb Interaction [S]

y
Consider a system of particles whose interaction potential falls o↵ like r as r ! 1. Show

that B2 is infinite if y  3. Comment.

M. R. Evans : February 12, 2019

 recall that there should be 3N normal

we
modes in total And so

fgqwtdw

fwmb.to du

b w5 Imax
I

b w MAY 3N
I

N s
waxy

b This

maximumfrequency defines a characteristic

temperature O through

KO KWMAX

KO t
Ev

Q ECEN


We now proceed to calculate the energythrough

E
Ftwglo not do

h
f Expbffydw

First consider the low T limit

Tk Op

Let uschange variables to x btw to

get the dependence on physical parameters out

of the integral and leave the dimensionless

integral as a constant

E
Yzf

t.es dx

Now T K
Op we can replace the upper

for

limit of the integral by infinityThen the

integral is equal to some finite constant

Thus at low temperatures Ext and the

heat capacity Cv at 5 as G ZE 2T

E b kÉ I I where I is the integral

sincetheintegralwill be

dom
small nated
x Strictly theerro
by will be xp
Cu
If 6bkI

introduced Ole Etty

I
Now we consider the high T limit To O
hw Max KB which implies two EBT 41
we expand
exp btw It btw to obtain
E h dw
b Witax
Eff be dw

15 b
3
FEC y
3 GET
NY
since
31
Cv 3 Nk which is equipartition for
2 3N harmonic oscillators
each oscillator has quadratic position and speed
dependence E KT
Using the density of modes we can write the
energy as
E
Jeff g w dw

We then need to calculate the density of modes

or phonon spectrum gas
Debye approximation
the spatial dimension We
is
gfÉwd
the prefuctor
where d is

AWd t
fix
glo by normalisation to a total tof Nd
modes fewDgcw dw Nd Nd Afew wd d w
Aqd
Now defining a
FIT and changing
int gration
variable to btw
x

wyatt Id Ed
Ndzk.tt f x where fix Ida EI
 E
IKEA dx

In the high temperature limit we have

hw Ik BT k I hence we can expand
btw It btw
KELI BEI
E
Ngata
11 57
d

fed
t
Yd I E ft de

g xd 1
E 7 E E
p fg
where we used the expansion

Fy l
y y t 2

dx
9 f x
d t l E x2 t t
914 EI Egg t
 4
YETI d East Iata
NAIL I I 12 3
Natya
Natty NEELI

EE
Iw NII 1 4 1

KWEI It Eats
IN dk
It data

hi
Previously we found
fla Fda Edt f 4 f
Here we can check what the corrections are

f x
f x Df a
Af x
SI EI de

É
de
f x
f Edge 1 doc

I find
Is e mad mg1amdétdy

É matfydé dy
Let m x da
y dy
T d 1 T dtt

Afca LEI doc Exdé dx

x I xdé Itd fade
From the notes
bar
Be far e
talk
1

I
for
e

Now d3r 4tr2dr

Be f 4m re 1 é Idr
e
Zafra 1 etc dr QED
The hard sphere potential is
givenby
e
It y
Bz Zag radr 2k3g 0 0 r a

o o rea
We sketch of assuming an attractive interaction
for r ro p kt rcr

Tf y l e
44kt
bet
pro

Kro
1 64 64 r ro

Bz Zafra I e 694J dr
21
Yt re Lieber dr

H
f r2dr 21T 26 r dr
3
Let bo 25
2513 3 Iraq end
90
affray
bo
Eq
 If q is ve attractive interaction for r
ro
then do is tve

Vander Waals equations of state

This is usually written P
Etf f
a

where b is a volume molecular size andrepresents

of
strong short range repulsion
The term up represents intermediate range
attraction
Expanding p NIV gives
P F KT I Yb a
F
From lectures we have F Fideal FIT B
P
PET
KT Ba ZE
Idealgas limit
KT bo
YI E E
NE It b I a
F
which agrees with expansion in density of van der
Waals equation
From lectures
s 3 S NK pET Bat
S
Nb pbo

Clearly if b so this is reduction from Ideal

Gas I E attractive interactions will encourage
particles to be closer together thus inducing
correlations in their position
Thepresence
of spatial correlations
reduces
missing
information and therefore the Gibbs entropy

r a r y 3
y
for

Bz Zafra I E 694J dr
ZITS re 1 é bro dr
 X 652
Hf My
2 1 r
2
6577 dr
2
2 652 dr
1
CELEBI
clearly if ya
GIIII
3 a

softie for larger

small r 1 e 69 1
1 eld 852
large r I 1 bry
r2 690
Bz 2
1 1 e do
I 24 where we have
27
ganger
introduced an
artificial
which r length
above
is a
large
Inspection of this integral reveals that it will
diverge for 23 due to the upper limit
y
regardless of particular value range
 dr r2 y
explicitly f
3 13
y
Ly r y

fur if y 3

00 as bar
if y 3
Clearly our perturbation theory breaks
down and we are dealing with a strongly
interacting system Note y 2 gives the
coulomb potential
which decay as 57
Actually potentials
known
y 63 are as
long range potential