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Stat Mech Mcquarrie ch3 5 Solns PDF
Stat Mech Mcquarrie ch3 5 Solns PDF
! is the partition function for the grand canonical ensemble, where T, V, ! are fixed. The characteristic potential
for the grand canonical ensemble is the grand canonical potential
" = E " T S " !N = "pV
(since E = T S " pV + !N )
q#
but ! = e
" = "kT ln !
so,
" = "kT ! q$ = "kT !
Starting with N,
2#mkT
h2
N ="
and p
p="
&
"
&
V
$
$
" 32
T ,V
T ,"
!"
V !e
= " (kT )
% 2$mkT & 32
h2
= kT
V ! exp
% 2$mkT & 32
h2
5
2
exp
2#m
h2
"
kT
"
kT
" 32
V ! exp
# ! $
kT
&
&
Putting those together we can get the ideal gas equation of state, namely
N
p = kT
V
Now S,
!
"
!
"3
!
"3 !
"
3
5
5
2#m 2
2#m 2
"!
"
!"
2
= k ! (kT ) 2
+
(kT
)
S="
V
e
V
e!"
2
T N,V
h2
h2
kT 2
1
((3-8-1))
"3
!
"3
2#mkT 2
! 2#mkT 2
!"
Ve "
V e!"
h2
T
h2
(
!
" '!
"3
5
2#mkT 2
!
!"
S=
k"
Ve
2
T
h2
)
*+
,
N
!
"
5
!
S=
k"
N
2
T
5
S = k!
2
((3-8-2))
"! 32
2#mkT
e = NV
h2
'!
"3 (
2#mkT 2 V
! = "kT ! ln
h2
N
!1
!"
1%
2$mkT
h2
& 32
V
N
! e2
This is the same expression as that obtained in the canonical ensemble (see Chapter 5). This is due to the
equivalence of ensembles when N is very large.
Problem 3-10
We are dealing with the isothermal-isobaric ensemble this time, with the partition function for an ideal monatomic
gas given to us in the problem as
'
(N
3
5
(2#m) 2 (kT ) 2
"=
ph3
# The isothermal-isobaric is for fixed (N, T, P ).
# The characteristic potential for this ensemble is the Gibbs free energy
G = E " T S + pV
# The thermodynamic properties are:
dG = "SdT + V dP + !dN
"
G
T p,N
!
"
G
V =
p T ,N
!
"
G
!=
N p,T
S="
# G is related to the isothermal-isobaric partition function " according to (see Table 3-1):
'
(
3
5
(2#m) 2 (kT ) 2
G = "kT ln " = "N kT ln
ph3
2
Starting with V,
3
4
3
5
3
2
G = "N kT ln (2#m) + ln (kT ) " ln h " ln p
2
V =
G
p
T ,N
NkT
p
(
3
5
(2#m) 2 (kT ) 2
5
S="
= N k ln
+ Nk
3
ph
2
p,N
'!
(
"3
# 5$
2#mkT 2 V
S = N k ln
+ N k ln e 2
2
h
N
!
G
T
'
"
S = N k ln
1%
2$mkT
h2
& 32
V
N
! e2
These are the same expressions as obtained in the grand canonical ensemble (Problem 3-8) and in the canonical
ensemble (see chapter 5). This is due to the equivalence of ensembles in the thermodynamic limit, i.e N is very large
such that fluctuations are negligible.
Problem 3-12
When looking at fluctuations, we derived
' %
&2 (
E "E
1
P ("E)
exp "
2kT 2 Cv
2#kT 2 Cv
For an ideal monatomic gas (derived explicitly in chapter 5)
3
E = N kT
2
E
3
Cv =
= Nk
T
2
We are now asked what is the probability that the N -particle system will sample an energy that differs by 10!4 %
from the average energy, E = 32 N kT ? (We can let N = NA = 6.022 % 1023M )
! !4 "
%
&3
10
E = 10!6 E = 10!6 N kT
"E =
100
2
% !6 &2 9 2 2 2
2
10
N k T
("E)
3 % !6 &2
4
=
=
10
N
3
2
2
4
2kT Cv
2kT ! 2 N k
So now we can go back to P ("E ),
6
5
1
3 % !6 &2
N
P ("E)
exp " 10
4
kT 3#N
3
7
8
1
Problem 3-18
Derive an expression for the fluctuation of the pressure in the canonical ensemble..
We know the pressure in state i is
!
"
Ei
pi = "
V
and by definition
7
8
9 % Ei &
i
" V exp !E
kT
7
8
p= i 9
i
exp !E
kT
i
pi exp
(pQ) =
V
V
kT
i
5
6.
:
Q
p
"Ei
p
pi exp
+Q
=
V
V
V
kT
i
.
5
6
5
6.
:
:
"Ei
"Ei
p
pi exp
exp
+Q
=
V
kT
V
V
kT
i
i
5
5
6
!
"
6
5
5
66
5
5
6
!
"
6
:
: pi
:
Ei
p
Ei
"Ei
"Ei
"Ei
1
1
p
pi exp
!"
!
!"
!
exp
+Q
=
exp
+
kT
V
kT
V
V
kT
kT
V
kT
i
i
i
Step 3: Divide through by the partition function
7
8
%
&
7
8
% E & 1 8
7 !E 82 9 7
97
9 1 pi
i
i
i
i
i
pi exp !E
p
!
"
!
! " E
!
exp !E
exp
p
V
kT
kT
V
kT
V
kT
Q V
i
i
i
+
=
+
Q
Q
Q
Q
!
"
2
p
p
pi
p2
+
=
+
kT
V
V
kT
Rearranging a little...
'!
" !
"(
p
p
i
& p2 = p2 " p2 = kT
"
V
V
#
pi
V
1
kT
has no immediate macroscopic interpretation, it must be calculate in any specific case and depends
# 2 $
i
on the particular spectrum of VE2i . This conclusion holds for all generalized forces in the form Ai = E
a , where
a is an extensive displacement conjugate to A. Hence, we cannot make an unqualified assertion that fluctuations in all
kinds of external forces will be small.
Note:
Compare this with fluctuations in extensive quantities such as E, H, or N which can be expressed in terms of
thermodynamic response variables suchs as heat capacities or compressibilities.
Specific calculations of the fluctuations in p of a perfect gas by Fowler is estimated as
(p " p2 )
5 % 10!12
p2
for a cubic centimeter of gas under standard conditions. This is approximately
molecules in the gas.
1
2
n3
(Source: The Principles of Statistical Mechanics, Richard C Tolman, Oxford University Press, first edition
1938)
Problem 3-24
Where the Ej s are the energies of the system when it has volume V. We also remember that H = E + pV.
Using the methods developed in class:
Step 1: Multiply both sides by the partition function
:
(Ej + pV ) e!!Ej !!pV
H" =
V,j
Step 2: Get the temperature derivative at constant (N, P ) (The conjugate variable to H in this case)
!
"
:
1 :
1
H
2
"+H 2
(Ej + pV ) e!!Ej !!pV =
(Ej + pV ) e!!Ej !!pV
T N,P
kT
kT 2
V,j
V,j
or
H2
H 2 " H = kT 2
but we know
H
T
N,P
H
T
"
= Cp . So,
2
H 2 " H = kT 2 Cp
5
N,P
Problem 3-26
Show that
"
N
V,T
V
= "N
2
p
V
N,T
..
SdT " V dp + N d! = 0
At constant T , we then get
!
d!
dp
"
d!
dp
"
d!
dN
"
V
N
V,T
dN
dp
"
V,T
d!
dN
"
V,T
V2
=" 2
N
dp
dV
"
N,T
Problem 4-2
Show that
6N
$V
h2
12mkT
$ 32
h = 6.6262 % 10!34 J ! s
J
k = 1.3807 % 10!23
K
me = 9.1095 % 10!31 kg
Putting those all together we get
6N
#V
h2
12mkT
" 32
= 1524 >> 1
Therefore Boltzmann statistics cannot be applied to electrons in metals. Must use Fermi-Dirac statistics.
6
Problem 4-6
S=
:
"
:
xn1 1 xn2 2
N=0 {nj }
"
9
99
means
Lets consider
"
9
{nj }
n1 n2
{nj }
"
:
n2
0
1
N
1
1
x1n1 x2n2 = x1 + x2
{nj }
"
:
n2
2
1
0
N
2
2
2
{nj }
"
:
n2
2
1
N
3
3
{nj }
"
:
n2
2
N
4
{nj }
For N > 4
"
9
{nj }
2
?
%
&
1 + xk + xk2
k=1
%
&%
&
S = 1 + x1 + x21 1 + x2 + x22 = 1 + x1 + x2 + x22 + x1 x2 + x21 + x1 x22 + x21 x2 + x21 x22
This expression contains the exact same terms as that obtained with
"
9
{nj }
xn1 1 x2n2 .
Problem 4-8
We need to show this ( remember the upper (lower) signs is for Fermi-Dirac (Bose-Einstein)
:
S = "k
:
j
[nj ln nj ( (1 ) nj ) ln (1 ) nj )]
Start with the partition function and go from there. Becuase of the equivalence of ensembles in the thermodynamic
limit, we can calculate the entropy using the ensemble
that offers the most mathematical
convenience. For Fermions
#
% ln ! & $
or Bosons, this is the grand canonical ensemble. S = k ln ! + kT T V,"
!=
?#
1 + $e
$ $1
! j
kT
ln ! = (
ln !
=(
T
#
! j $
ln 1 + $e kT
! j
$#e kT
1 ( $e
! j
kT
:
j
#
:
! j $
S=k
( ln 1 ( $e kT +
j !"
kT 2
exp
!(j !")
kT
! j
1 ( $e kT
#
$
!"
$e!!j jkT
1 ( $e!!j
To make this a little easier to manipulate we can write this shorthand by making the following substitutions. Let:
u = 1 ( $e!!j and v = $e!!j
u = 1 ( v and u ) v = 1
v
nj =
u
So we now have
S=k
:
j
S=k
:
j
{( ln u " nj ln v} = k
Remembering that u ) v = 1
S =k
:
j
S = "k
{( ln u " nj ln nj " nj ln u}
:3
j
! "
4
1
" nj ln nj
u
{nj ln nj ( (1 ) nj ) ln (1 ) nj )}
8
Problem 4-12
N-distinguishable independent particles, each of which can be in state +o or -o .
N+ = number of particles with energy +o
N! = number of particles with energy "o
with N+ + N! = N
The total energy is given as:
E = N+ o " N!o = 2N+ o " N o
% &
We now have to evaluate the partition function Q by summing exp !E
over levels and compare it to the result
kT
Q = q N ..
# We know
!
"
:
"Ej
Q=
exp
kT
j
where j labels a state in which the system can reside.
# Instead of summing over the states that the system can be in, we can also sum over the possible energy levels,
making sure we take account of the degeneracy of each energy level, i.e.
!
"
:
"E
Q=
#(E) exp
kT
E
N+
So we have
!! 2o
if we let x = e
or
Q = e!No
:
N+
% !!2 &N+
N!
o
e
N+ (N " N+ )!
#Now we need to compare this to Q = q N , where q is the single particle partition function defined as
9
q=
e!!l
where l labels the single particle states. In this example there are two single particle states, with energy -o
and +o .
= q = e!!o + e!o
and
%
&N
Q = q N = e!!o + e!o
#The last part of this problem asks us to calculate and plot the heat capacity for this system. We know Cv =
and E is given as
%
&
ln e!!o + e!o
ln Q
2
= kT N
E = kT
T
T
! !!o
"
o !!o
o !o
" 2e
e
" e!o
2e
E = kT 2 N kT !!o kT
N
=
o
e
+ e!o
e!!o + e!o
2
Cv
Nk
vs.
kT
o
# $
# $2
E
o
o
2
= Nk
sech
T
kT 2
kT
10
E
T
Problem 5-4
Calculate the entropy of Ne at 300K and 1 atm.
# The entropy of an ideal gas (eqn 5-20):
S = N k ln
'!
2#mkT
h2
" 32
V e2
N
and
V
kT
=
= 4.0889 % 10!26
N
p
!
"3
2#mkT 2
= 8.852 % 1031
h2
%
&
S = N k ln 4.41 % 107
1%
&N 2
S = k ln 4.41 % 107
%
&N
# = 4.41 % 107
which makes sense since it should be large because N is on the order of 1023.
Problem 5-9
What is the DeBroglie wavelength of Ar at 298K?
!
%=
h2
2#mkT
Use:
m = 6.634 % 10!26 kg
k = 1.3807 % 10!27 Jk
h = 6.6262 % 10!34 J ! s
11
" 12
12
% V & 13
N
Problem Set 5
Additional Problems Solutions
3.20 MIT
Dr. Anton Van Der Ven
Fall
2001
Fall 2002
Problem 1
(a) A system of N non-interacting particles with two possible states either 0 or . A good rule is too assume
particles (e.g. atoms, electrons, etc) are indistinguishable unless they are localized in a crystal or on a surface. The
number of atoms in the excited state can be determined using Boltzmann statistics under the assumption that we are
working at high temperature and/or low density::
N = N #
where # is the probability an atom will be in state . This probability is determined using the single particle
partition function and can be written as
7 ! 8
exp kT
7 8
# = 9
exp !;
kT
(McQuarrie 4-14)
But our system can be in only two states, so the sum in the denominator can be found explicitly:
7 ! 8
exp kT
7 ! 8
# =
exp [0] + exp kT
So N can be written as
7 ! 8
exp kT
N
7 ! 8 =
7 8
N = N # = N
1 + exp kT
1 + exp kT
N =
1+exp[ kT
U =N
:
i
# i i = N (# 1 1 + # 2 2 ) = N [(1 " # 2 ) ! 0 + # 2 ! ]
U = N (# 2 ) = N
U=
7 ! 8 .
exp kT
7 ! 8
1 + exp kT
1+exp[ kT
Note: Since many particles will occupy the same state (either 0 or ) these particles must be Bosons. At lower
temperatures we would have to use Bose-Einstein statistics (McQuarrie 4-26) which would lead to a much more
complicated problem since we would have to determine the chemical potential !.
1
Problem 2
The magnetization is given as
M =
N
:
ni !o
i=1
#This is basically saying that we have atoms localized in a crystal and the magnetic moment at each site can be
either up or down. The problem asks us to determine the thermodynamic properties as a function of T, N, H. Let us
also assume for simplicity that we can work at constant volume. Therefore, our controlling variables are T, N, V, H.
#We need to make the appropriate Legendre transform to the entropy. Remember the entropy can be written
starting from E:
E = T S " pV + HM + !N
rearranging to get things in terms of S and ( we get
S
= (E + (pV " (HM " (!N
k
Legendre transform such that our controlling variables are V, N, T, H
S
" (E + (HM = ( (T S " E + HM ) = "() = ln &
k
where ) is the characteristic potential for this ensemble with V, N, T, H constant and & is the partition
function. & can be written as
:
&=
exp ["( (Estate " Mstate H)]
states
where we sum over all possible energy states and magnetizations Mstate.
#Since the particles are non-interacting, the energy at N, ( = constant and H = 0 is constant. E is independent
of the number or arrangement of up versus down spins. Since the absolute scale of energy is not important for
thermodynamics, we can arbitrarily set the constant energy equal to zero giving us
' N
(
N
:
:
:
: ?
ni !o H =
&=
exp [(Mstate H] =
exp (
exp [(ni!o H ]
states
n1 ,n2 ,...n N
&=
N
?
i=1
exp [(ni !o H ] =
N
?
+1
:
exp [(ni !o H ]
i=1 ni =!1
We know the characteristic potential of an ensemble is related to the partition function for that ensemble according
to
"() = ln & ) = "kT ln &
Furthermore, we know from thermo that
d) = "SdT " pdV + !dN " M dH
which gives us the following relationships for the properties of the system:
S
M
=
=
"
"
!
!
2
)
T
)
H
"
V,N,H
"
V,N,T
! =
p =
"
)
N V,T ,H
!
"
)
"
V T ,N,H
S="
)
T
"
V,N,H
$
"o H
(exp [(!o H ] " exp ["(!o H ])
" kT
2
exp [(!o H ] + exp ["(!o H ]
#The last part of this problem asks you to determine the behavior of the energy and entropy as T 0.
EH (T 0) = "N !o H
lim S = lim kN {ln (exp [(!o H ] + exp ["(!o H ]) " (!o tanh ((!o H )} = 0
N
:
!o ni
i=1
&=
where s = states
We want to determine the fluctuations in the extensive quantity M. Use the 3-step procedure developed in class.
Step 1: Multiply both sides by the partition function
:
M& =
states
Because Es is always constant (see comment in Problem 2) we can therefore arbitrarily set it to zero and write
N
:
M& =
n1 ,n2,...n N
N
:
!o ni
i=1
.-
'
exp (!o H
N
:
ni
i=1
.(.
M
&+M
H
N
:
n1 ,n2 ,...n N
N
:
!o ni
i=1
.-
'
exp (!o H
N
:
i=1
ni
.(.0
N
:
n1 ,n2 ,...n N
!o
N
:
i=1
ni
.2 -
'
exp (!o H
N
:
i=1
M
2
+ (M = (M 2
H
or we can write it like this
F
with:
!
M
H
(*M )
"
!,N
= M2 " M =
1 M
( H
I
H
= (N !2 1 " tanh2 ((!H )
F
G
2
= !2 {1 " 1} = 0. In other
(c) As ( , tanh ((!H ) 1. Therefore M T 0 = N ! and (*M )
T 0
words, the ground state with all the spins aligned has no fluctuations.
4
ni
.(.
Problem 4
From the first and second law we have
dE = T dS " pdV + HdM + !dN
(Euler Form)
E = T S " pV " HM + !N
We are working with fixed N, T, V, M in this problem. We need to make a Legendre transform because T is a
controlling variable instead of E.
S
" (E = "(F = ln Q
k
:
Q=
exp ["(Estate ]
states
F = "kT ln Q
From the differential form of F, namely
dF = "SdT " pdV + HdM + !dN
we get that
H=
F
M
"
T ,V,N
N
:
i=1
where n+ = number of up spins and n! = number of down spins. That means that the sum in the expression
of Q must be performed over only those states with fixed M (i.e. fixed n+ and n!)
#Also the atoms in the system do not interact, meaning that the energy is independent of the number and
arrangement of up/down spins and is therefore constant = Eo.
:
:
Q=
exp ["(Estates] =
exp ["(Eo ] = # exp ["(Eo ]
states with
magnetization M
states with
magnetization M
where # is the number of states that are consistent with a magnetization M = !o (n+ " n!) .
N!
n+ ! (N " n+ )!
N!
Q=
exp ["(Eo ]
n+ ! (N " n+ )!
!
"
!
"
N!
N!
F = "kT ln
exp ["(Eo ] = Eo " kT ln
n+ ! (N " n+ )!
n+ ! (N " n+ )!
#=
M + !o N
2!o
we can substitute this back into our expression for F to get F as a function of M
3
!
" !
"
!
"4
M + !o N
M + !o N
!o N " M
!o N " M
F = Eo " kT N ln N "
ln
ln
"
2!o
2!o
2!o
2!o
5
% F &
Remembering that H = M
T ,V,N
!
"
3
!
"
!
"
4
1
1
1
1
F
M + !o N
!o N " M
"
H=
= "kT "
ln
+
+
ln
2!o
2!o
2!o
2!o
2!o
2!o
M T ,V,N
3 !
"
!
"4
kT
M + !o N
!o N " M
ln
H=
" ln
2!o
2!o
2!o
!
"
M + !o N
2!o (H = ln
!o N " M
and it is easy to show that M = !o N tanh (!o (H ) which is the same result as in the other ensemble of Problems
2 and 3. This is due to the equivalence of ensembles in the thermodynamic limit.
Problem 5
(a) Grand canonical ensemble:
!=
N =0
:
j
exp ["(Ej ]
exp [(!N ] =
)
*+
,
This sum extends
over allstates with
total # of particles = N
:
j
N =0
qN
N!
for a one component gas of non-interacting particles. We can write q in closed form as we have done before as
!
"3
2#mkT 2
q=
V
h2
So now ! can be written as:
!=
% !" &N
:
:
qe
qN
exp [(!N ] =
N!
N!
N=0
N=0
But if we let a = qe!" then we can write this sum in a form for which the solution is know, namely
:
aN
= ea
N!
N=0
z=
with
e!"
h2
2#m
(
" 32
"
!
"
"
(zV )
= kT
= kT z
p="
V T ,"
V
! "
! "
"
z
= kT
N ="
V = zV
! T ,V
!
putting those two parts together and eliminating z gives us the familiar ideal gas equation p =
kT N
.
V
(c)
J
(*+)
=
+2
(*N )
N2
(because V fixed)
N! = ! =
N=0
q N !"N
e
N!
:
:
q N !"N
q N !"N
=
N
e
N
e
N!
N!
N=0
N=0
N
!
"
!+N
!
N=0
N
!
"
q N !"N
(N
e
N!
N=0
! + (N ! N ! = (N 2 !
(N 2
N 2 " N = zV
z
N
= 2
V
V
+2 " +2
N
= 2
+2
N
K
J
+2 " +2
1
kT
= =
pV
+
N
+2 " +2 =
q N !"N
e
N!
1
2
(*N )
2