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ii
Preface
iv
Preface
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1
Introduction to Statistical Physics
1=2
1=3
( N1 )2
1=2
1
;
N 1=6
for large N .
4- Consider an event of probability p. The probability of n
occurrences of this event out of N trials is given by the binomial
distribution,
WN (n) =
N!
pn (1
n!(N n)!
p)N
WN (n) ! P (n) =
n!
exp (
);
A)
0.16
0.14
0.12
PN(N1)
0.1
0.08
0.06
0.04
0.02
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.6
0.7
0.8
0.9
N1/N
0.06
B)
0.05
P(N1)
0.04
0.03
0.02
0.01
0
0
0.1
0.2
0.3
0.4
0.5
N1/N
Graphs of P N(N1) (dots) versus N1/N, and the corresponding Gaussian distribution (solid
line), for N=36 (top figure) and N=216 (at bottom).
P (n) = exp (
n=0
hni =
1
X
n!
n=0
1
X
nP (n) = exp (
n=0
= exp (
= 1;
1
X
n=0
@
@
and
( n)2 = (n
1
X
n=0
n!
n!
= ;
hni)2 = :
N2 + N3
N 1 + N3
and P (B) =
;
N
N
P (AB)
and
P (AB) = P (B) P (A j B) = P (A) P (B j A) :
(viii) Considering a third event C, show that
P (B j A)
P (B) P (A j B)
=
;
P (C j A)
P (C) P (A j C)
which is an expression of Bayestheorem.
6- A random variable x is associated with the probability
density
p (x) = exp ( x) ;
for 0 < x < 1.
(a) Find the mean value hxi.
(b) Two values x1 and x2 are chosen independently. Find
hx1 + x2 i and hx1 x2 i.
(c) What is the probability distribution of the random variable y = x1 + x2 ?
*** Note that
hxi = 1;
and that
p (y) =
Z Z
hx1 + x2 i = 2;
hx1 x2 i = 1;
x1
x2 ) :
N
X
j=1
sj ;
where fsj g is a set of independent, identical, and identically distributed random variables, given by the probability distribution
"
#
(s l)2
1=2
2
exp
w(s) = 2
;
2 2
where and l are positive constants. After N steps, what is
the average displacement from the origin? What is the standard
deviation of the random variable x? In the large N limit, what
is the form of the Gaussian distribution associated with this
problem?
*** It is easy to see that
hxi = N hsi = N l;
and
(x
hxi)2 = N (s
hsi)2 = N
w(s)ds = 1;
hxi = N hsi = 0;
( x)2 =
N
:
12
t) = P (N1
1; t) W1 + P (N1 + 1; t) W2 ;
(N1
N
1)
and W2 =
N1 + 1
:
N
N1 P (N1 ; t) :
N1
2
N
hN1 it + 1;
2
N
N
;
2
100
90
N1 (t)
80
70
60
50
40
0
50
100
150
200
250
t (passos)
300
350
400
450
500
Figura 1: Simulation for the Ehrenfest urn model. Graph of N1 versus the discrete time
t, for N=100 and the initial condition N10=N. The solid line represents the theoretical
result for the time evolution of the average value of N1.
10
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2
Statistical Description of a Physical
System
1. Neglect the complexities of classical phase space, and consider a system of N distinguishable and noninteracting particles, which may be found in two states of energy, with = 0
and > 0, respectively. Given the total energy U of this system,
obtain an expression for the associated number of microscopic
states.
*** Suppose that there are N0 particles in the ground state
and Ne particles in the excited state. The number of accessible
microscopic states of this system is given by
(U; N ) =
N!
;
N0 !Ne !
where N0 + Ne = N and U = Ne .
2. Calculate the number of accessible microscopic states of
a system of two localized and independent quantum oscillators,
with fundamental frequencies ! o and 3! o , respectively, and total
energy E = 10~! o .
*** There are three microscopic states:
(n1 = 2; n2 = 2), (n1 = 5; n2 = 1), and (n1 = 8; n2 = 0).
12
3. Consider a classical one-dimensional system of two noninteracting particles of the same mass m: The motion of the
particles is restricted to a region of the x axis between x = 0
and x = L > 0. Let x1 and x2 be the position coordinates of the
particles, and p1 and p2 be the canonically conjugated momenta.
The total energy of the system is between E and E + E. Draw
the projection of phase space in a plane dened by position coordinates. Indicate the region of this plane that is accessible to
the system. Draw similar graphs in the plane dened by the
momentum coordinates.
4. The position of a one-dimensional harmonic oscillator is
given by
x = A cos (!t + ') ;
where A; !; and ' are positive constants. Obtain p (x) dx, that
is, the probability of nding the oscillator with position between
x and x + dx. Note that it is enough to calculate dT =T , where T
is a period of oscillation, and dT is an interval of time, within a
period, in which the amplitude remains between x and x + dx.
Draw a graph of p(x) versus x.
*** It is easy to show that
1
1
p (x) =
2 A
x
A
1=2
Now consider the classical phase space of an ensemble of identical one-dimensional oscillators with energy between E and
E + E. Given the energy E, we have an ellipse in phase space.
So, the accessible region in phase space is a thin elliptical shell
bounded by the ellipses associated with energies E and E + E,
respectively. Obtain an expression for the small area A of this
elliptical shell between x and x + dx. Show that the probability
p(x)dx may also be given by A=A, where A is the total area of
the elliptical shell. This is one of the few examples where we can
check the validity of the ergodic hypothesis and the postulate
of equal a priori probabilities.
13
5. Consider a classical system of N localized and weakly interacting one-dimensional harmonic oscillators, whose Hamiltonian
is written as
N
X
1 2 1 2
H=
p + kx ;
2m j 2 j
j=1
where m is the mass and k is an elastic constant. Obtain the
accessible volume of phase space for E
H
E + E, with
E << E. This classical model for the elastic vibrations of a
solid leads to a constant specic heat with temperature (law of
Dulong and Petit). The solid of Einstein is a quantum version of
this model. The specic heat of Einsteins model decreases with
temperature, in qualitative agreement with experimental data.
*** The volume in classical phase space is given by
=
4m
k
N=2
Vsph;
E H E+ E
EN :
The dependence on N is more delicate (it requires the calculation of the volume of the hypersphere).
6. The spin Hamiltonian of a system of N localized magnetic
ions is given by
N
X
H=D
Sj2 ;
j=1
where D > 0 and the spin variable Sj may assume the values 1
or 0, for all j = 1; 2; 3:::. This spin Hamiltonian describes the
eects of the electrostatic environment on spin-1 ions. An ion
in states 1 has energy D > 0, and an ion in state 0 has zero
14
(U; N ) =
U
D
X
N
U
D
1
;
N !N !
U
!
D
U
!
D
u
ln 2
D
u
ln 1
D
u
D
u
u
ln ;
D D
N!
:
N !N0 !N+ !
(U; N ) =
N0 ;N+ ;N
N!
;
N !N0 !N+ !
15
(U; N ) =
N!
N
N =0
U
D
U=D
N!
U
D
U
D
U
D
!N
N
U
D
=0
U
D
!N !
!
!N !
N0 ;N+ ;N
N!
N !N0 !N+ !
N!
;
e !N
e0 !N
e+ !
N
1;
(N0 + N+ + N
2)
N) +
= ln
2
N!
+
N !N0 !N+ !
(DN+ + DN
U) :
U
;
D
e0 = N
N
u
ln 2
D
u
ln 1
D
u
D
u
u
ln ;
D D
16
in agreement with the limiting result from the previously obtained exact expression for . In slightly more complicated problems, without an exact solution, we will be forced to resort to
similar maximization techniques.
7. In a simplied model of a gas of particles, the system is
divided into V cells of unit volume. Find the number of ways to
distribute N distinguishable particles (with 0 N V ) within
V cells, such that each cell may be either empty or lled up
by only one particle. How would your answer be modied for
indistinguishable particles?
*** If we consider distinguishable particles, we have
d
V!
:
(V N )!
(V
V!
;
N )!N !
so that
1
ln i v ln v (v 1) ln (v 1) ;
N
in the thermodynamic limit (note that v = V =N
1). This is
a simplied, and fully respectable, model of a non-interacting
lattice gas. The entropy per particle is given by
s = s (v) = kB [v ln v
(v
1) ln (v
1)] ;
kB ln (1
) = kB
1
2
+ ::: :
17
This is a virial expansion. The low-density limit gives the wellknown expression for the ideal gas.
8. The atoms of a crystalline solid may occupy either a position of equilibrium, with zero energy, or a displaced position,
with energy > 0. To each equilibrium position, there corresponds a unique displaced position. Given the number N of
atoms, and the total energy U , calculate the number of accessible microscopic states of this system.
*** It easy to see that
(U; N ) =
N!
! N
Additional exercises
9. Obtain an expression for the volume of a hypersphere of radius R in d dimensions. Use this expression for obtaining ti=1 he
volume (E; V; N ; E) in phase space associated with a gas of
N non-interacting classical monatomic particles, inside a box of
volume V , with energy between E and E + E (with E << E).
What is the entropy S = S (E; V; N ) of this system? Is there
any trouble in the thermodynamic limit?: How to correct this
trouble? What is the Gibbs paradox?
*** The volume of the hypersphere is calculated in Appendix
A4. We then present an alternative calculation. The element of
volume of a d-dimensional hypersphere can be written as
+1
+1
Z
Z
A dR =
dx1 :::
dxd R x21 x22 :::x2d d R2 ;
1
i=1
i=1
18
1
2
+1
Z
i=1
dk exp
+1
Z
"
ik R
N
X
x2i
i=1
!#
d=2
dk exp
ikR
ik
N + O (ln N ) ;
xn e x dx = n!
19
f (x0 )]g dx = C;
20
xo + 21 "
exp fn [f (x)
1
"
2
xo
Z
Z
1
"
2
xo
xo
1
"
2
xo
1
"
2
xo
exp fn [f (x)
f (x0 )]g dx
Therefore,
" exp [ n ]
In
C;
which leads to
" exp [ n ] exp [nf (x0 )]
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3
Overview of Classical
Thermodynamics
@
@p
=
T
kB T
;
p
@
@T
=
p
d o
p
+ kB ln
dT
po (T )
kB T dpo
;
po (T ) dT
22
pv:
=T
T
@2p
@T 2
:
v
Use this result to show that the specic heat of an ideal gas does
not depend on volume. Show that
@
@p
@ T
@T
=
T;N
:
p;N
@cV
@v
@s
@T
=)
v
@2s
@
@2s
=T
=T
=T
@T @v
@v@T
@T
@s
@v
:
T
sdT
pdv =)
=)
@s
@v
s=
=
T
@f
@T
p=
@p
@T
@f
@v
;
v
kB T
23
fo (T ) exp
kB T
p
;
fo (T )
3a
2
1=4
1=2
1=4
and
2
p
=
T
3
3a
2
1=4
1=2 3=4
4
3
3a
2
1=4
v 1=2 u3=4 + c;
24
"
3a
= v2T 4
2
4
T
3
1=4
3a
2
3a 2 4
v T
2
v 1=2
3=4
+c :
*** Let us consider a similar problem, with a slight modication in one of the equations of state,
3
u = pv
2
p = avT n :
and
Note that, instead of T 4 , we are writing T n , where n is an arbitrary integer. Is this a bona de thermodynamic system? Is it
possible to have n 6= 4?
Again, we rewrite the equations of state in the entropy representation,
1
=
T
3a
2
1=n
2=n
1=n
p
2
=
T
3
and
1=n
3a
2
1+2=n 1 1=n
@s
@u
;
v
p
=
T
@s
@v
=)
u
@ 1
@v T
@ p
@u T
=
u
;
v
1=n
2
v
n
1+2=n
1=n
2
=
3
3a
2
1=n
1+2=n
1
n
1=n
25
and
1
=
T
@s
@u
p
=
T
@s
@v
1
= a1=4 v 1=4 u
2
1
= a1=4 v
4
1=2
3=4 1=2
cf
f:
T2
26
CH
cH T
H;
=
s
@ (T; s) @ (T; H)
@ (T; s)
=
=
@ (H; s)
@ (T; H) @ (H; s)
@s
@H
1
T
@s
@T H
Ts
Hm =) dg =
sdT
mdH;
@g
@T
; m=
H
@g
@H
=)
T
@s
@H
=
T
@m
@T
:
H
27
dh = T ds + vdp =) T =
@h
@p
and v =
p
:
s
@T
@s
=
p
T
> 0:
cp
Also, we have
@2h
@p2
=
s
@v
@p
< 0:
It is straightforward to use standard tricks (Jacobians, for example) to write an expression for the adiabatic modulus of compressibility,
1 @v
;
s =
v @p s
in terms of positive quantities.
*9. Show that the entropy per mole of a pure uid, s =
s (u; v), is a concave function of its variables. Note that we have
to analyze the sign of the quadratic form
d2 s =
1 @2s
@2s
1 @2s
2
(du)
+
dudv
+
(dv)2 :
2 @u2
@u@v
2 @v 2
@2s
@u2
@2s
@u@v
du dv
@2s
@u@v
@2s
@v 2
du
dv
@2s @2s
+
@u2 @v 2
@2s @2s
@u2 @v 2
@2s
@u@v
= 0:
28
@2s
@u@v
>0
@2s @2s
+
> 0:
@u2 @v 2
Now it is straightforward to relate these derivatives of the entropy with positive physical quantities (as the compressibilities
and the specic heats).
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4
Microcanonical Ensemble
1
ln
N
(E; N ) ;
30
4. Microcanonical Ensemble
u
ln 1
D
u
D
u
u
ln ;
D D
2D exp ( D)
;
1 + 2 exp ( D)
A ln
v
vo
4. Microcanonical Ensemble
31
a
;
v
N1 ;N2
and
N!
N1 !N2 !
;:::
X
j Nj
= E:
Except for an additive constant, show that the entropy per particle is given by
!
!
X N
~j
~j
N
ln
;
s = kB
N
N
j
n o
~j is the set of occupation numbers at equilibrium.
where N
Using the continuum limit of the Boltzmann gas, show that the
entropy depends on temperature according to a term of the form
kB ln T (note the correction!).
32
4. Microcanonical Ensemble
1
ln
N
(E; N )
kB
~j
N
N
ln
~j
N
N
1;
2)
N!
+
= ln Y
Nj !
j
Nj
j Nj
so that
ej = exp (
N
ej
exp (
N
=X
N
exp (
2 j) ;
2 j)
2
:
j)
ej
N
E
=
= u;
j
N
N
4. Microcanonical Ensemble
33
@
Z1 ;
@ 2
Z1 =
exp (
2 j) :
p2
2
2m
2 m
3=2
3 1
3
= kB T;
2 2
2
kB
d3 !
p
p2
2m
exp
Z1
p2
2m
exp
ln
Z1
3
= kB ln T + constant;
2
which should be compared with the entropy per particle for the
ideal gas (pv = kB T , u = 3kB T =2),
3
s = kB ln T + kB ln v + constant.
2
Note that s ! 1 for T ! 0, which is a well-known di culty
of classical statistical mechanics.
5. Consider a lattice gas of N particles distributed among V
cells (with N V ). Suppose that each cell may be either empty
or occupied by a single particle. The number of microscopic
states of this system will be given by
(V; N ) =
V!
:
N ! (V N )!
34
4. Microcanonical Ensemble
(v
1) ln (v
1)] ;
ln 1
1
v
1
1
1
+ 2 + 3 + :::
v 2v
3v
Note that Bolyles law is already given by the rst term is this
expansion.
In order to nd =T , we write the thermodynamic entropy
S = N s = S (V; N ), and take the partial derivative with respect to N . Note that we can nd ratios, as p=T and =T , but
we cannot nd an independent expression for the temperature
(since there is no mention to the energy in the denition of this
very simple and schematic model).
It is instructive to draw a graph of =T versus the particle
density = 1=v (remember that 0 < < 1). Note that is an
increasing function of . Also, note that =T ! 1 for ! 0; 1
(in the vacuum).
*** This lattice gas model can be alternatively dened in
terms of a set variables fti g, i = 1; :::; V , such that ti = 1 if cell
i is occupied, and ti = 0 if cell i is empty. The total number of
accessible states (V; N ) is given by a (restricted) sum over the
congurations of these occupation variables,
X
(V; N ) =
1;
fti g;restriction
4. Microcanonical Ensemble
V
X
35
ti = N:
i=1
36
4. Microcanonical Ensemble
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5
Canonical Ensemble
N
X
i=1
Si2
oH
N
X
Si ;
i=1
38
5. Canonical Ensemble
0), sketch graphs of the internal energy, the entropy, and the
specic heat versus temperature. Indicate the behavior of these
quantities in the limits T ! 0 and T ! 1. Calculate the
expected value of the quadrupole moment,
* N
+
1 X 2
S ;
Q=
N i=1 i
as a function of eld and temperature.
*** The canonical partition function is given by
"
#
N
N
X
X
X
Z=
exp
D
Si2 + o H
Si =
i=1
fSi g
"
exp
S1 ;S2 ;:::;SN
(
X
N
X
i=1
Si2 +
oH
i=1
DS 2 +
exp
o HS
D) cosh (
o H)
)N
Si =
i=1
= f2 exp (
N
X
+ 1gN :
In this simple case, the thermodynamic limit is trivial. The internal energy per ion comes from
u=
1 @
ln Z:
N@
1 @
ln Z;
N @H
1 @
ln Z:
D @D
5. Canonical Ensemble
39
oH
i i+1
N
X
i;
i=1
i=1;3;5;:::;N 1
(T; H) =
@m
@H
:
T
1; 2
i=1
i odd
ig
exp [ J
1 2
oH
)N=2
2 )]
40
5. Canonical Ensemble
= [2 exp ( J) cosh (2
o H)
+ 2 exp (
J)]N=2 :
ig
sinh (2 o H)
;
cosh (2 o H) + exp ( 2 J)
1
ln Z;
N
@f
@T
:
H
1
kB J tanh J;
2
5. Canonical Ensemble
41
) + exp ( 3
)]N :
= ~! o n +
1
2
; with n = 1; 3; 5; 7; ::::
3
~! o
exp
2
:
1 exp ( 2 ~! o )
42
5. Canonical Ensemble
@
3
2~! o
ln Z1 = ~! o +
@
2
exp (2 ~! o )
N
X
i=1
1 2 1
p + m! 2 qi2 :
2m i 2
+1
Z
1
dq1 :::
+1
Z
1
dqN
+1
Z
1
dp1 :::
+1
Z
1
dpN exp [
H] =
5. Canonical Ensemble
8+1 +1
<Z Z
:
dpdq exp
2m
p2
9N
=
m! 2
=
q
;
2
43
7. Consider again the preceding problem. The canonical partition function can be written as an integral form,
Z1
Z( )=
(E) exp ( E) dE;
0
+i1
Z
Z ( ) exp ( E 0 ) d =
i1
Z1
1
dE (E)
2
+i1
Z
exp [ (E 0
E)] d =
(E 0 ) :
i1
+i1
Z
i1
exp N ln
2
!
ln + u
d ;
44
5. Canonical Ensemble
2 u2
1=2
exp N ln
2
!
+ ln u + 1
2
!
+ ln u + 1;
N
X
i=1
1 2
p + V (qi ) ;
2m i
8 1
< 2 m! 2 q 2 ;
:
1
m! 2 q 2
2
for q > 0;
+ ; for q < 0;
with > 0.
(a) Obtain the canonical partition function of this classical
system. Calculate the internal energy per oscillator, u = u (T ).
What is the form of u (T ) in the limits ! 0 and ! 1?
(b) Consider now the quantum analog of this model in the
limit ! 1. Obtain an expression for the canonical partition
function. What is the internal energy per oscillator of this quantum analog?
*** The classical partition function is given by Z = Z1N , where
Z1 =
[exp (
) + 1] :
5. Canonical Ensemble
45
46
5. Canonical Ensemble
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6
The Classical Gas in the Canonical
Formalism
1. A system of N classical ultrarelativistic particles, in a container of volume V , at temperature T , is given by the Hamiltonian
N
X
H=
c j~pi j ;
i=1
N
X
i=1
1 2 1
p~ + m! 2 xni ;
2m i
2
48
where n is a positive and even integer. Use the canonical formalism to obtain an expression for the classical specic heat of
this system.
*** Note that the canonical partition function may be written
as Z = Z1N , where
Z1 =
1=2
2 m
2
m! 2
n=2
+1
dy exp ( y n ) :
1
Thus,
@
n+2
ln Z1 =
kB T:
@
2n
u=
1
1
p~12 + p~22 +
j~r1
2m
2
~r2 j2 ;
j~r1
~r2 j2
1=2
1
p~ 2 + p~22 + jr12
2m 1
ro j ;
~r2 j. What
2 m
d r1
d3 r2 exp
j!
r1
2
!
r2 j
2 m
3=2
49
from which we obtain the Helmholtz free energy (and the value
of D). It interesting to check the constant value of the molecular
specic heat, c = (9=2) kB .
The second Hamiltonian represents a more complicated model
of a diatomic molecule. The partition function is given by
Z
3Z
2 m
3
d r1 d3 r2 exp [
j(j!
r1 !
r2 j ro )j]
Z1 =
3
2 m
V I;
where
I=4
Zro
r2 exp [
(ro
r)] dr+4
Z1
r2 exp [
(r
ro )] dr =
ro
2ro2
4
(
2
3
)4
exp (
ro ) :
50
ma2
=
4
"
d
dt
d'
dt
sin2
p2'
p2
+
:
ma2 ma2 sin2
Therefore,
1
1
urot = hHrot i = kB T + kB T = kB T:
2
2
In the presence on an electric eld (taken along the z direction),
and with the magnetic moment along the axis of the rotator, we
have
p2'
p2
H=
E cos :
+
ma2 ma2 sin2
The associated partition function is given by
Z1 =
Z2
d'
+1
Z
1
dp
+1
Z
+ E cos ] =
dp' exp [
p2
ma2
p2'
+
ma2 sin2
4 2 ma2 2 sinh ( E)
:
E
Thus, we have
h cos i =
coth (
E)
1
= L(
E
E) ;
51
Z1
0
r dr
sin d
Z2
d' exp
m! 2o 2
r + qEr cos
2
0
3=2
2
exp
m! 2o
The polarization is given by
=
hqr cos i =
q2E 2
2m! 2o
1 @
q2E
ln Z1 =
;
@E
m! 2o
so the dielectric susceptibility is just a constant (in sharp contrast to the previous result for permanent electric dipoles!)
6. The equation of state of gaseous nitrogen at low densities
may be written as
pv
B (T )
=1+
;
RT
v
52
Z1
r2 fexp [
V (r)]
1g =
=2
Za
0
r dr
Zb
r2 [exp ( Vo )
1] dr:
This is page 53
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7
The Grand Canonical and Pressure
Ensembles
exp (
Ej +
Nj ) :
Show that this same form of entropy still holds in the pressure
ensemble (with a suitable probability distribution).
2. Consider a classical ultrarelativistic gas of particles, given
by the Hamiltonian
N
X
H=
c j~pi j ;
i=1
54
1
8 V
ZN =
N ! (h c)3
1
X
exp (
N ) ZN = exp
N =0
8 V
exp (
(h c)3
) ;
1 8 V
exp (
(h c)3
):
8 v
z
(h c)3
ln z;
f (zo ) = 1
ln
(h c)3
:
8 v
55
hNj i2 = z
2 m
3=2
and
( N )2 = z
@
zV
@
z ln ( ; z) = 3
@z @z
h
2 m
3=2
= hN i :
p
The relative deviation is thus of order 1= N .
5. Show that the average quadratic deviation of energy in the
grand canonical ensemble may be written as
( E)2 = Ej2
hEj i2 =
@U
@
;
z;V
56
can
= N kB T 2 cV
@N
@
T;V
"
since
( N )2 = kB T
@U
@N
@N
@
T;V
#2
> 0;
> 0:
T;V
(No
N
:
N ) a (T )
57
No !
exp (
N ! (No N )!
. We then
N) :
X
N
No !
exp (
N ! (No N )!
N ) z N = [z exp (
) + 1]No ;
No z
z + exp (
).
for n = 0; 1; :::.
Also, note the thermodynamic limit,
1
ln
V
! ln (1 + z) +
ln z;
for z > 1
58
and
1
ln ! ln (1 + z) ; for z < 1:
V
For z > 1, we have the equations of state
ln z;
and
1
z 2 + (1 + z)
=
:
v
z (1 + z)
p
= ln (1 + z) ;
kB T
and
1
z
=
:
v
1+z
p
= ln (1 + z) +
kB T
For z < 1, we have
This is page 59
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8
The Ideal Quantum Gas
1. Obtain the explicit forms of the ground state and of the rst
excited state for a system of two free bosons, with zero spin,
conned to a one-dimensional region of length L. Repeat this
problem for two fermions of spin 1=2.
*** The p
single-particle states are given by ' (x) = A sin (kx),
where k = 2mE=~ and kL = n , with n = 1; 2; 3:::. Note that
' (x) vanishes at x = 0 and x = L.
The ground state is given by C sin ( x1 =L) sin ( x2 =L), where
C is a normalization constant.
The rst excited state is given by
D [sin ( x1 =L) sin (2 x2 =L) + sin (2 x1 =L) sin ( x2 =L)] :
kB
X
j
ffj ln fj
(1
fj ) ln (1
fj )g ;
60
1
exp [ (
)]
pV =
1X
ln [1 + z exp (
j )] :
V
(2 )3
Z1
~2 k 2
2m
4 k 2 dk ln 1 + z exp
4 k 2 dk
~2 k 2
2m
~2 k 2
2m
V
4 3
k ln 1 + z exp
3f
3
(2 )
=
2
+
3
Z1
exp
~2 k 2
2m
+1
2 X
3 j z
j
1
exp (
j)
+1
2
U;
3
61
1 2
p~
2m
o;
"
N
V
~2
2 m
3=2
62
z exp (
A
j) = z
(2 )2
Z1
~2 k 2
+
2m
2 k exp
= kB T ln
NA
A
~2
2 m
o:
A,
we
n+
1
2
~!
x n+
1
2
~!;
63
d2
S ( ) + O x2 ;
S( )d 2
where
S( )=
1
X
exp
n+
n=0
with
1
2
h
i
= 2 sinh
2
@
~!
ln Zv
@
and c = kB
~!
kB T
@2
ln Zv ;
@ 2
2 (r
ro )
a
2 exp
ro
a
where Vo = 7 10 19 J, ro = 8 10 11 m, and a = 5 10 11 m.
Sketch a graph of V (r) versus r. Calculate the characteristic
temperatures of vibration and rotation to compare with experimental data (see table on Section 8.4).
*** Note that
and
dV
= 0 for r = ro
dr
d2 V
dr2
=
ro
2Vo
> 0;
a2
64
~2
~2
=
=
;
2kB I
2kB M ro2
2Vo
a2 M
1=2
~
=
kB
2Vo
a2 M
1=2
This is page 65
Printer: Opaque this
9
The Ideal Fermi Gas
2N
5V
~2
5m
2=3
N
V
5=3
1
V
@V
@p
3m
~2 6
2=3
2
V
N
5=3
66
*** At zero temperature, the expected value of the (singleparticle) energy is calculated in terms of the density of states
D ( ). With D ( ) = C 1=2 , we have
R F
D( )d
3
h i = R0 F
= F:
5
D( )d
0
Note that
h i=
1 !2
mv
2
6 F
!
v2 =
5m
2 F
!
v 2x =
;
5m
d=2
d
2
67
1
exp (
)+1
we have
N=
Ld
(2 )d
= L
1
Cd
2
d
2m
~2
d=2
d=2 1
f ( )d =
D( )f ( )d ;
1
d
2 (2 )
2m
~2
Cd
d=2
d
2
= kB T ln
p
where v = V =N is the volume per particle, and = h= 2 mkB T
is the thermal wavelength. Sketch a graph of =kB T versus T .
Obtain the rst quantum correction to this result. That is, show
that the chemical potential of the ideal quantum gas may be
written as the expansion
3
kB T
ln
= A ln
+ B ln
+ :::;
68
z exp (
1 2
z exp ( 2
2
j)
=z
exp (
1 2X
z
exp ( 2
2
j
j)
j)
j)
3=2
= V
ln
cl
=z V
mkB T
2 ~2
3=2
cl
=z V
mkB T
2 ~2
3=2
Thus,
z = exp (
)=
N
V
2 ~2
mkB T
3=2
69
= kB T ln
with
V
v=
N
and
1=2
2 ~2
mkB T
=p
h
:
2 mkB T
Check that the same result can be obtained in the classical formalism of the grand ensemble, with the introduction of the correct Boltzmann counting, N !, and of the quantum dimensional
correction" of the classical phase space, h3N .
The rst quantum correction of this result is given by
3=2
=z V
mkB T
2 ~2
mkB T
2 ~2
3=2
N =z V
ln
3=2
mkB T
4 ~2
1 2
z V
2
+ O z3 :
Thus,
3=2
mkB T
4 ~2
z2 V
+ O z3 ;
N
V
=z
23=2
z2 + O z3 :
z=
v << 1,
+A
and
3
+A
+ :::
1
23=2
"
v
1
23=2
+A
#2
70
Therefore,
ln z = ln
"
+A
= ln
23=2 v
kB T
ln
23=2 v
Z 1
m
U= A
f ( )d ;
2 ~2 0
with the Fermi-Dirac distribution,
f( )=
1
exp [ (
)] + 1
Note that exp (x) = [exp (x) + 1]2 is an even function of x, and
that
Z 1
exp (x) dx
d
1
= 1:
2 dx =
dx exp (x) + 1
1 [exp (x) + 1]
71
Also, we have
Z1
1
f ( )d !
2
1
(
)2
1
1
1
1
exp (x)
+
[exp (x) + 1]2
x2 exp (x) dx
1
2g =
2
[exp (x) + 1]
1+
1
(
)2 3
2 ~2
m
N
A
72
1=3
= ~c
N
V
1=3
and
3
U = N F:
4
The asymptotic form of the specic heat at low temperatures comes from a straightforward application of Sommerfelds
method. We should note that
Z 1
Z
3
1 3 1
x
exp (x) dx
2
f ( )d =
dx !
1+
3
[exp (x) + 1]2
0
1
3
!
and
Z
1
f ( )d =
4
!
where
1+6
1
1
exp (x) dx
dx !
[exp (x) + 1]2
7 4 1
;
15 ( )4
)2
3 (
)2
1+
2
1
4
1+
7 4
exp (x) dx
dx
=
:
15
[exp (x) + 1]2
and
3 1
U= N 3
4 F
1+
2
4
1+6
3 (
)2
(
1
)2
7 4 1
:
15 ( )4
73
and
U = VC
3=2
f ( )d ;
where
f( )=
1
exp [ (
)] + 1
74
1=2
2
f ( )d !
3
3=2
+1
1+
3=2
exp (x)
dx;
[exp (x) + 1]2
1
3
I4
+O
128 ( )4
where
I0 =
+1
1
1
(
)6
g;
exp (x)
dx = 1;
[exp (x) + 1]2
+1
2
x2 exp (x)
;
dx
=
2
3
1 [exp (x) + 1]
Z +1
x4 exp (x)
7 2
I4 =
d
x
=
;
15
[exp (x) + 1]2
1
I2 =
3=2
F
3=2
1+
3 2 1
7 2 1
1
+
) ;
2
4 + O(
24 ( )
640 ( )
( )6
1 + M2
T
TF
+ M4
T
TF
+O
"
T
TF
#)
75
We left for the reader the task of obtaining the numerical coefcients (M2 and M4 ). It is then easy to write an expansion of
the internal energy in terms of (even) powers of (T =TF ).
8. Consider a system of free fermions in d dimensions, with
the energy spectrum
a
~
~k; = c k ;
where c > 0 and a > 1.
(a) Calculate the prefactor A of the relation pV = AU .
(b) Calculate the Fermi energy as a function of volume V and
number of particles N .
(c) Calculate an asymptotic expression, in the limit T << TF ,
for the specic heat at constant volume.
*** In the thermodynamic limit, we have
Z 1
Ld
Cd k d 1 ln [1 + z exp ( ck a )] dk =
pV = ln =
(2 )d 0
Z
Ld
ca 1
k d 1+a
=
C
dk:
d
d 0 z 1 exp ( ck a ) + 1
(2 )d
Also, we have
U=
Thus,
@
Ld
Cd c
ln ( ; z; V ) =
@
(2 )d
k d 1+a
dk:
z 1 exp ( ck a ) + 1
a
pV = U:
d
In order to derive the Fermi energy, we write
Z 1
Ld
kd 1
@
C
dk;
N = z ln ( ; z; V ) =
d
@z
z 1 exp ( ck a ) + 1
(2 )d
0
76
Ld
Cd
(2 )d
1
acd=a
d
a
d:
= cp
BH
X
!
k
= ln
+ ln
ln f1 + z exp [
(c~k
We then write
N =z
@
ln
@z
= N+ + N ;
B H)]g :
with
V
N = 2
2
Z1
1
~c
f ( )d ;
where
f ( )=
77
1
exp [ (
BH
) + 1]
1
~c
BH
d +
F + BH
For
BH
= 3
<<
2 1=3
+3
2
B H)
=3
(~c)3
N
:
V
(H = 0), we have
~c
N
V
1=3
2
B
3 (3
2 )5=3
~c
N 1=3
V
H2 + O H4 :
(N+
N );
which leads to
3
M=
(3
2 )1=3
2
BN
~c
N 1=3
V
H + O H3 ;
1
N
@M
@H
=
H=0
2
B
(3 2 )1=3 ~c
N 1=3
V
78
10. In the classical paramagnetic theory of Langevin, proposed before the advent of quantum statistics, we assume a
classical Hamiltonian, given by
N
X
H=
~i
N
X
~ =
H
i=1
H cos i ;
i=1
Z1N
d exp (
H cos )
H) ;
1
x
d exp (
H cos ) = 2
sin exp (
H cos ) d =
4
H
sinh (
79
H) :
Thus,
1
+ coth (
H
M =N
H) = N L (
H) ;
1
n+
2
f (x) dx +
1 0
f (0) :
24
*** The grand partition function for this system was written
as
Z
1
eHL2 X L
ln = 2
hc n=0 2
~2 kz2
2m
ln 1 + z exp
+1
dkz
1
He
mc
n+
1
2
~2 kz2 He
+
x;
2m
mc
80
so that it becomes easy to integrate over kz . In the second integral, we just call = ~2 kz2 =2m. It is now straightforward to
obtain an expression for the zero-eld susceptibility [check the
excellent article by R. B. Dingle, "Some magnetic properties of
metals. I. General introduction and properties of large systems
of electrons", Proc. Roy. Soc. A211, 500 (1952)].
This is page 81
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10
Free Bosons: Bose-Einstein
Condensation; Photon Gas
V
3
5
g5=2 (z)
2
where
=p
kB T
g3=2 (z) ;
h
2 mkB T
and
g (z) =
1
X
zn
:
n
n=1
g3=2 (z)
:
g1=2 (z)
82
15
v
kB 3 g5=2 (1)
4
T 3=2 ;
15 g5=2 (1)
3
kB
> kB :
4
g3=2 (1)
2
Ld
(2 )d
Z1
0
Cd k d 1 dk
exp
0~
2 k2
2m
;
1
where Cd = 2
we have
d=2
83
(2 )1=2 ~2 N 2 1
kB T0 =
2m
Ld Cd I
where
I=
Z1
2=d
xd=2 dx
:
exp (x) 1
~k;
~2 k 2
+
2m
where
= 0; 1. Obtain an expression for the BoseEinstein
condensation temperature as a function of the parameter 1 .
*** In the grand-canonical formalism, above the temperature
of condensation, the number of bosons is given by
N=
X
j
1
exp (
X
~k;
1
exp
~2 k 2
2m
(2 mkB T )3=2
g3=2 (z) + g3=2 ze
h3
:
1
84
c~k)] :
x3 dx
:
exp (x) 1
X
~k;j
1
2
85
=
n
(1
Y X
!
k ;j
n!
k ;j
exp
n!
k ;j
exp 4
~k;j
~!~k;j
n=0
1
n+
2
1 5
=
2
1
Y exp
~ck
2
=
:
exp ( ~ck)
! 1
k ;j
1X
~ck
2!
k ;j
X
!
k ;j
ln [1
exp (
~ck)] ;
86
1 X
1 @
ln Z =
N@
N
~k;j exp
~!~k;j
:
1
~!~k;j
d+1
4kB
(4
~2 c2 )d=2
(d + 1) (d + 1)
d
2