0% found this document useful (0 votes)
131 views7 pages

PH4211 Outline Solutions 2007: E E E E E

This document contains solutions to questions from a PH4211 Outline exam. Key points include: 1) Entropy is defined as S and the number of microstates is Ω. Systems evolve to states of greater entropy and probability. 2) For a composite system, the total number of microstates Ω is the product of the individual microstates. At equilibrium, the temperatures of the two systems will be equal. 3) Fluctuations in energy σE are proportional to the heat capacity CV. In the thermodynamic limit, fractional fluctuations go to zero as 1/N.

Uploaded by

Roy Vesey
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
131 views7 pages

PH4211 Outline Solutions 2007: E E E E E

This document contains solutions to questions from a PH4211 Outline exam. Key points include: 1) Entropy is defined as S and the number of microstates is Ω. Systems evolve to states of greater entropy and probability. 2) For a composite system, the total number of microstates Ω is the product of the individual microstates. At equilibrium, the temperatures of the two systems will be equal. 3) Fluctuations in energy σE are proportional to the heat capacity CV. In the thermodynamic limit, fractional fluctuations go to zero as 1/N.

Uploaded by

Roy Vesey
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 7

PH4211 Outline Solutions 2007

Question 1

a) S is the entropy. Ω is number of microstates in the macrostate. [2]

b) For an isolated system all microstates are equally probable. So probability of


observing a macrostate is proportional to the number of microstates corresponding to
it. State observed is the most probable one, so it is the state of greatest entropy. Upon
removing a constraint the system will evolve to a more probable state – it will evolve
to a state of greater (maximal) entropy. [2]

c) Ωa(Ea) is no of microstates in system a when it has energy Ea. And Ωb(Eb) is no of


microstates in system b when it has energy Eb. Total number of microstates of the
composite system is Ω = ΩaΩb. Let Et be the total energy of the composite system,
denote Ea by E and then Eb is Et – E, so that
  a ( Ea )b ( Eb )  a ( E)b ( Et  E) .
Must maximise this by varying E. So differentiate and set equal to zero
da db
b  a  0.
dE dE
or
d ln a d ln b

dE dE
but S = k lnΩ, so we get Ta = Tb, where
dE
T .
dS
Total derivatives here, since only heat energy is allowed to flow. [4]

Total energy of the composite system is fixed but energy can flow back and forth
between the two. Probability of a energy partition is given by Ω. It will be sharply
peaked at the equilibrium energy value. [1]

d) This is the square root of the average of the square of the deviations of E from its
mean value. It has the dimensions of energy and measures the extent of the deviations
from the mean. [2]

e)
E  
2
σ E2   E 2  2E E  E
2
E
[2]
 E2  2 E  E  E2  E
2 2 2

f)
1  E j / kT
Pj 
e
Z
is probability of Ej state. Here Z is the normalisation constant, known as the partition
function – since probabilities must sum to unity.

1
Mean value given by summing over probabilities
1 1
E   Pj E j   E j e j .
 E / kT
[2]
Z j Z j
g)
Starting from
1
E   E je j
 E / kT

Z j
we see that we could get at E 2 by differentiating with respect to temperature so that
another Ej comes down in the summation. It is simpler to get the Z on the left hand
side first.
E  e j   E je j .
 E / kT  E / kT

j j

We differentiate this with respect to temperature (at constant volume):


 E E 1
 e j  2  E j e j  2  E 2j e j .
 E / kT  E / kT  E / kT

T j kT j kT j
This is then divided by the partition function, to give
 E
2
E E2
  ,
T kT 2 kT 2
or
E
E 2  E  kT 2
2
.
T
This may be written as
E 2  E  kT 2 CV
2

so that
 E  kT 2CV .
Or do it in terms of β = 1/kT. Easier. [3]

h) Since CV is extensive, proportional to N, then fractional fluctuations


E N
 1 N .
E N
So fractional fluctuations go to zero in the thermodynamic limit. [2]

2
Question 2

(a) Classical expression for partition function – integrating over p and q. Exponent is
Hamiltonian / kT. Hamiltonian is total energy T + V, both expressed as functions of p
and q. The powers of h are to specify the size of the cells in phase space. The N!
accounts for indistinguishable particles – multiple occupancy is not considered. [3]

(b) Ideal gas partition function is


 pi2 
   kT
1  
3N 
Zid  e  i 2m 
d3 N p d3 N q
N !h
since here U = 0. But now can do integral over q, giving VN:
 pi2 
   kT
VN  
3N 
Zid  e  i 2m 
d3 N p
N !h
So Z then factorises as Z = ZidQN where
 U  qi , q j  kT
1
QN  N  e i j d3 N q .
V
The VN thus arises from the integration over q. [4]

(c) F = -kTlnZ and p = -F/V. So p = kTlnZ/V. Then


  ln Zid  ln QN 
p  kT   
 V T , N V T , N 
but first part gives ideal gas behaviour (or can show explicitly) so that
 N  ln QN 
p  kT   . [4]
V V T , N 
(d) Argument of exponential in partition function is either zero or infinity for q > σ or
q < σ. So there is no dependence on T. So partition function has no dependence on T.

Then
p N  ln QN
 
kT V V N
and the rhs is independent of temperature. This means that the only free variables for
the rhs are V, N. The lhs is intensive; V/N is the only intensive combination.
So p/kT = fn(N/V) [3]

pV V  ln QN
(e)  1 .
NkT N V N
Clearly  ln QN V depends on σ and can depend on N/V. Overall we require that
V
 ln Q V be dimensionless so σ and N/V must combine as Nσ3/V.
N

-- Virial expansion, Padé approximants, molecular dynamics. [3]

(f) No transition to a liquid since the fluid can’t be self-bound as there is no attractive
part to the interaction. But could be a solid phase; molecular dynamics indicate so. [3]

3
Question 3

(a) Order parameter – measure of the order in the system, zero in disordered phase.
Order parameter varies discontinuously in a first-order transition and continuously in
a second-order transition. [3]

(b) Order parameter is polarisation P. Odd terms in the free energy expansion vanish
if the lattice has inversion symmetry (or because P is a vector while F is a scalar).
Expansion terminated at 6th order. Need the 6th term because the 4th term may be
negative, while we require the system to be stable / φ bounded. [3]

(c)
f (φ)
f (φ) h h
s

t c
φ
φ

a l

h: high temp. t: transition temp. c: critical temp. l: low temp.


First order Second order [4]

(d) If F4 coefficient is negative then we need the F6 term (with a positive coefficient)
so that φ is bounded. The sextic curve is the first-order form above.
If F4 coefficient is positive then since φ is assumed small the F6 term can be neglected
and the system will be stable. And the quartic curve is the second-order form above.
[3]

(e)
f (φ)

t
φ
Δφ Transition state

At the transition temperature the three minima are level. Write:


F  F2 2  F4 4  F6 6
The transition point is characterised by the conditions
bg
F  0 and
dF
d
0

or

4
F2 2  F4 4  F6 6  0
2 F2  4 F4 3  6 F6 5  0.
We know we have the   0 solution; this can be factored out. The others are found
from solving the simultaneous equations
F2  F4 2  F6 4  0
F2  2 F4 2  3F6 4  0.
The solution to these is
F4
2  
2 F6
or
F4

2 F6
as we know that F4 is negative.

This gives the discontinuity in the order parameter at the transition since  will jump
from zero to this value at the transition. Thus we can write
F4
  .
2 F6

  0 as F4  0 as expected. [4]

(f) F2 vanishes at the critical point since the free energy is then a pure quartic. Lineat
temperature dependence is simplest and F2 must be +ve in the high-temp disordered
phase.
F  a T  Tc   2  F4 4  F6 6 .
Entropy:
F
S ,
T
so that
F
S   0  a 2 .
T
The latent heat is
L  Ttr S
 aTtr  2 .
So that latent heat as
F4
L  aTtr .
2 F6
L  0 as F4  0 and transition becomes 2nd order. [3]

5
Question 4

(a) i Order parameter is magnetisation M.


ii Order parameter is non-conserved
iii Rotational symmetry broken
iv Continuous symmetry broken
v Transition is 2nd order. [5]

(b) B = Bext + b , so that

M  M B b
 tanh  0 ext 
M0  N kT 
but b = λM and we want the spontaneous magnetisation in the absence of the external
Bext. Then
M  M M 
 tanh  0 
M0  N kT 
which can be written as
M  M Tc 
 tanh  
M0  M0 T 
where
Tc   M 02 Nk .
Tc is the transition temperature / Curie temperature. [9]

(c)
1.0

M/M0

0.5

0.0
0.0 0.5 1.0 T/Tc

M is continuous at the Tc so the transition is 2nd order. [2]

(d)   NkTc M 02 so b  NkTc M M 02 . Put M M 0 ~ 1 .


Then b ~ NkTc M 0 . M 0  2 N B - here μB is Bohr magneton. So
kTc 1.4 1023 1043
b~   788T .
2B 2  9.27 1024
Dipole field is many orders of magnitude less than this. Explanation is Heisenberg
exchange interaction. [4]

6
Question 5

Essay question.

Must cover microscopic and macroscopic description of states. Very large number of
microstates compatible with a macrostate necessitates the adoption of a statistical
approach.

Microcanonical – Isolated system – Boltzmann entropy S = klnΩ – all microstates


equally likely.

Canonical – thermal contact with a reservoir (T replaces E as proper variable) – Gibbs


entropy S = –kΣjPjlnPj – probability of microstate  exp – Ej/kT.

Can obtain canonical from microcanonical by regarding (canonical) system plus


reservoir as isolated (microcanonical).

Partition function Z = Σj exp – Ej/kT. Helmholtz free energy F = –kTlnZ.


F = E – TS, so dF = –SdT – pdV + μdN. From this we obtain S, p, μ from
S  F T , p  F V ,   F N .

So we can obtain all thermodynamic properties from the partition function – and that
just needs knowledge of the microscopic energy levels.

You might also like

pFad - Phonifier reborn

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


Alternative Proxies:

Alternative Proxy

pFad Proxy

pFad v3 Proxy

pFad v4 Proxy