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333: Statistical Mechanics I Problem Set # 6 Solutions Fall 2003

The Microcanonical Approach

1. Classical Harmonic Oscillators:

(a) The volume of accessible phase space for a given total energy is proportional to

1
Z
Ω= N dq1 dq2 · · · dqN dp1 dp2 · · · dpN ,
h H=E

where the integration is carried out under the condition of constant energy,

N  2
mω 2 qi2

X pi
E = H ({qi , pi }) = + .
i=1
2m 2

Note that Planck’s constant h, is included as a measure of phase space volume, so as to

make the final result dimensionless.
The surface of constant energy is an ellipsoid in 2N dimensions, whose area is difficult
to calculate. However, for N → ∞ the difference between volume and area is subleading in
N , and we shall instead calculate the volume of the ellipsoid, replacing the constraint H =
E by H ≤ E. The ellipsoid can be distorted into a sphere by a canonical transformation,
changing coordinates to

√ pi
qi0 ≡ mωqi , and p0i ≡ √ .
mω

The Hamiltonian in this coordinate system is

N
ω X 02
H ({qi0 , p0i }) pi + qi02 .


E= =
2 i=1

Since the canonical transformation preserves volume in phase space (the Jacobian is unity),
we have
1
Z
Ω≈ N dq10 · · · dqN
0
dp01 · · · dp0N ,
h H≤E
p
where the integral is now over the 2N -dimensional (hyper-) sphere of radius R = 2E/ω.
As the volume of a d-dimensional sphere of radius R is Sd Rd /d, we obtain
N N
2π N
 
1 2E 2πE 1
Ω≈ · = .
(N − 1)! 2N hω hω N!

1
The entropy is now given by
 
2πeE
S ≡ kB ln Ω ≈ N kB ln .
N hω

(b) From the expression for temperature,


1 ∂S  N kB
≡ ≈ ,
T ∂E N E

we obtain the energy

E = N kB T,

and the heat capacity

C = N kB .

(c) The single particle distribution function is calculated by summing over the undesired
coordinates and momenta of the other N − 1 particles. Keeping track of the units of h
used to make phase space dimensionless, gives
1
R
(H≤EN −1 ) hN −1
dq2 · · · dqN dp2 · · · dpN dp1 dq1
p(p1 , q1 )dp1 dq1 = R 1 × ,
(H≤E) hN
dq1 dq2 · · · dqN dp1 dp2 · · · dpN h

where EN −1 = E − p21 /2m − mω 2 q12 /2. Using the results from part (a),

Ω (N − 1, EN −1 )
p(p1 , q1 ) =
hΩ(N, E)
N −1
p21

2 N −1 π N −1 mω 2 2


hω (N −1)!
E− − 2m 2
q1
=
2 N πN N


h hω N! E
p21
!N −1
mω 2 2
ω N + q 1
= 1 − 2m 2
.
2π E E

Using the approximation (N − 1) ∼ N , for N  1, and setting E = N kB T , we have

p21 2
!N
ω N 2m + mω 2 q 2
1
p(p1 , q1 ) = 1−
2π N kB T N kB T
p2 2
!
ω 1
+ mω q 2
1
≈ exp − 2m 2
.
2πkB T kB T

2
Let us denote (p1 , q1 ) by (p, q), then

p2 mω 2 q 2
 
ω
p(p, q) = exp − − ,
2πkB T 2mkB T 2kB T

is a properly normalized product of two Gaussians. The mean kinetic energy is

 2 Z
p p2 kB T
= p(p, q) dqdp = ,
2m 2m 2

while the mean potential energy is also

mω 2 q 2 mω 2 q 2
  Z
kB T
= p(p, q) dqdp = .
2 2 2

********

2. Quantum Harmonic Oscillators:

(a) The total energy of the set of oscillators is
N
!
X N
E = h̄ω ni + .
i=1
2

Let us set the sum over the individual quantum numbers to

N
X E N
M≡ ni = − .
i=1
h̄ω 2

The number of configurations {ni } for a given energy (thus for a given value of M ) is
equal to the possible number of ways of distributing M energy units into N slots, or of
partitioning M particles using N − 1 walls. This argument gives to the number of states
as
(M + N − 1)!
Ω= ,
M ! (N − 1)!
and a corresponding entropy
    
M +N −1 M N −1
S = kB ln Ω ≈ kB (M + N − 1) ln − M ln − (N − 1) ln .
e e e

(b) The temperature is calculated by

! !
 E N N
+ −1 E+ 2 h̄ω
 
1 ∂S  kB M +N −1 kB h̄ω 2 kB
≡ ≈ ln = ln E N
≈ ln N
.
T ∂E N h̄ω M h̄ω h̄ω
− 2
h̄ω E− 2
h̄ω

3
By inverting this equation, we get the energy
 
N exp (h̄ω/kB T ) + 1 1 1
E = h̄ω = N h̄ω + ,
2 exp (h̄ω/kB T ) − 1 2 exp (h̄ω/kB T ) − 1

and a corresponding heat capacity

  2
∂E  h̄ω exp (h̄ω/kB T )
C≡ = N kB 2.
∂T N kB T [exp (h̄ω/kB T ) − 1]

(c) The probability that a particular oscillator is in its nth quantum level is given by
summing the joint probability over states for all the other oscillators, i.e.

Ω N − 1, E − (n + 21 )h̄ω
P
(E−(n+1/2)h̄ω) 1


X
p(n) = p(ni ) = P =
{ni6=1 } (E) 1 Ω(N, E)

[(M − n) + N − 2]! M ! · (N − 1)!

= ·
(M − n)! · (N − 2)! (M + N − 1)!
M (M − 1) · · · (M − n + 1) · N
≈
(M + N − 1)(M + N − 2) · · · (M + N − n − 1)
≈ N (M + N )−n−1 M n ,

where the approximations used are of the from (I − 1) ≈ I, for I  1. Hence,

 −n−1  n
E N E N
p(n) = N − +N −
h̄ω 2 h̄ω 2
!n
E N
N h̄ω − 2
= E N E N
,
h̄ω + 2 h̄ω + 2

which using
! !n
N h̄ω E N
E+ +
 
1 kB 2 h̄ω 2 nh̄ω
= ln N h̄ω
, =⇒ E N
= exp − ,
T h̄ω E− 2 h̄ω − 2
kB T

leads to the probability

   
h̄ω h̄ω
p(n) = exp −n 1 − exp − .
kB T kB T

(d) As found in part (b),

 
h̄ω

h̄ω
2 exp kB T
Cquantum = N kB i2 .
kB T
h  
h̄ω
exp kB T − 1

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In the high temperature limit, h̄ω/(kB T )  1, using the approximation ex ≈ 1 + x for
x  1, gives
Cquantum = N kB = Cclassical .

At low temperatures, the quantized nature of the energy levels of the quantum oscillators
becomes noticeable. In the limit T → 0, there is an energy gap between the ground state
and the first excited state. This results in a heat capacity that goes to zero exponentially,
as can be seen from the limit h̄ω/(kB T )  1,
 2  
h̄ω h̄ω
Cquantum = N kB exp − .
kB T kB T

********

3. Hard Sphere Gas:

(a) The available phase space for N identical particles is given by

1
Z
Ω= d3 q~1 · · · d3 q~N d3 p~1 · · · d3 p
~N ,
N !h3N H=E

where the integration is carried out under the condition,

N N
X p2i X
E = H(~
qi , p
~i ) = , or p2i = 2mE.
i=1
2m i=1

The momentum integrals are now performed as in an ideal gas, yielding

(2mE)3N/2−1 2π 3N
Z
Ω= · 3N

· d3 q~1 · · · d3 q~N .
N !h3N 2 − 1 !

The joint integral over the spacial coordinates with excluded volume constraints is best
performed by introducing particles one at a time. The first particle can explore a volume
V , the second V − ω, the third V − 2ω, etc., resulting in
Z
d3 q~1 · · · d3 q~N = V (V − ω)(V − 2ω) · · · (V − (N − 1)ω).

Using the approximation (V − aω)(V − (N − a)ω) ≈ (V − N ω/2)2 , we obtain

 N
Nω
Z
3 3
d q~1 · · · d q~N ≈ V − .
2

5
Thus the entropy of the system is
"   3/2 #
e Nω 4πmEe
S = kB ln Ω ≈ N kB ln V − .
N 2 3N h2

(b) We can obtain the equation of state by calculating the expression for the pressure of
the gas, 
P ∂S  N kB
= ≈ ,
T ∂V E,N
 V − N2ω
which is easily re-arranged to,
 
Nω
P V − = N kB T.
2
Note that the joint effective excluded volume that appears in the above expressions is one
half of the total volume excluded by N particles.
(c) The isothermal compressibility is calculated from

1 ∂V  N kB T
κT = − = > 0,
V ∂P T,N
 P 2V

and is explicitly positive, as required by stability constraints.

********

4. Interacting Rod-Molecules:

excluded
volume
2l

(a) Including both forms of entropy, translational and rotational, leads to

"  N #    
1 N Ω(θ) N −1 Ω(θ)
S = kB ln V − A(θ) ≈ N kB ln n − + 1 + ln A(θ) .
N! 2 2

(b) The extremum condition ∂S/∂θ = 0 is equivalent to

Ω0 A0
= ,
2n−1 − Ω A

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where primes indicate derivatives with respect to θ. Solving for the density gives

2A0
n= .
ΩA0 + Ω0 A

(c) Elementary geometry yields

Ω = l2 (θ + sin θ) ,

so that the equilibrium condition becomes

2 −1
n = f (θ) = 2
[θ (2 + cos θ) + sin θ] ,
l
with the function f (θ) plotted below:
f(θ)

nc

0 θ θc π
(d) At high densities, θ  1 and the equilibrium condition reduces to

V
N≈ ;
2θl2
the angle θ is as open as allowed by the close packing. The equilibrium value of θ increases
as the density is decreased, up to its “optimal” value θc at nc , and θ (n < nc ) = θc . The
transition occurs at the minimum of f (θ), whence θc satisfies

d
[θ (2 + cos θ) + sin θ] = 0,
dθ
i.e.
2 (1 + cos θc ) = θc sin θc .

********