PHYS 522: Statistical Mechanics

Homework #2

Prakash Gautam
Oct 30, 2018

1. We mentioned in class that in calculating the matrix of e−βH , ⟨1, 2, 3, N |e−βH |1, 2, 3, N ⟩, permutation
goth the particle coordinates in the first wave function and energy states in the second yields a result
which is N! of the result for a fixed set of {k, } states that is, without permuting the energy states. Do it
explicitly of two particle and two state case starting with ua (1)ub (2).
Solution:
The general matrix element for N particle n state system from Pathria eq (5.5.12) is
[ ] [ ]
−βH ′ ′ 1 ∑ − βℏ2 k2 ∑ ∑ {
∗ ∗
}
⟨1, . . . , N |e |1 , . . . , N ⟩ = e 2m δp {uk1 (p1 ) . . . ukn } . . . δp uk1 (p1 ) . . . ukn
N! p p
k

For two particle and two sate we get

1 ∑ − βℏ2 k2
⟨1, 2|e−βH |1′ , 2′ ⟩ = e 2m [ua (1)ub (2) ± ua (2)ub (1)] [u∗a (1)u∗b (2) ± u∗a (2)u∗b (1)]
2!
k

Multiplying the wavefunctions we get

1 ∑ − βℏ2 k2
⟨1, 2|e−βH |1′ , 2′ ⟩ = e 2m [ua (1)ub (2)u∗a (1)u∗b (2) ± ua (1)ub (2)u∗a (1)u∗b (2)
2!
k
+ua (1)ub (2)u∗a (1)u∗b (2) ± ua (1)ub (2)u∗a (1)u∗b (2)

For the case of fixed {ki }, i.e., if only the particles are permuted
1 ∑ − βℏ2 k2
⟨1, 2|e−βH |1′ , 2′ ⟩ = e 2m [ua (1)ub (2)u∗a (1)u∗b (2) ± ua (1)ub (2)u∗a (1)u∗b (2)]
2!
k

But since the density operator is hermition, the matrix elements are equal to the complex conjugate of
itself with the coordinate exchanged
∗
⟨1, 2|e−βH |1′ , 2′ ⟩ = ⟨1, 2|e−βH |2′ , 1′ ⟩

This would essentially mean

ua (1)u∗a (1′ )ub (2)u∗b (2′ ) = ua (2)u∗a (2′ )ub (1)u∗b (1′ )
ua (2)u∗a (1′ )ub (1)u∗b (2′ ) = ua (1)u∗a (2′ )ub (1)u∗b (2′ )

Using this in the sum we get

1 ∑ − βℏ2 k2
⟨1, 2|e−βH |1′ , 2′ ⟩ = e 2m [ua (1)ub (2) ± ua (2)ub (1)] [u∗a (1)u∗b (2) ± u∗a (2)u∗b (1)]
2!
k
∑ βℏ2 k2
= e− 2m [ua (1)ub (2)u∗a (1)u∗b (2) ± ua (1)ub (2)u∗a (1)u∗b (2)]
k

Here the last expression is exactly twice the expression for fixed {ki }case. Where 2 is equal to the factorial
of itself 2! = 2 thus the rusult is N ! times the expression for fixed {ki } case. □

1
2. Study the density matrix and the partition function of a system of free particles, using un symmetrized
wave function instead of symmetried wave function. Show that, following the text procedure, on encounters
neighter th Gibbs’ correction factor N1 ! nor a spatial correlation among the particles.
Solution:
If we used unsymmetrized wave function rather than symmetrized wave function we get
∑ ℏ2 k 2
⟨1, 2, . . . , N |e−βH |1, 2, . . . , N ⟩ = e−β 2m (uk1 (1) . . . ukn (N ))(u∗k1 (1′ ) . . . u∗kN (N ′ ))
k
∑ 2 2
2 k1 +...+kN
= eβℏ 2m (uk1 (1) . . . ukn (N ))(u∗k1 (1′ ) . . . u∗kN (N ′ ))
k1 ,...kN

The summation in the exponential can now be changed into product of the exponential and the expression
becomes
N [
∏ { }]
e−βℏ uki (i)u∗kj (j ′ )
2
/2m
=
i=1

Since the states are dense we can change the summation over ki by the integration
( ) 3N ( )
−βH m 2
m ( ′ 2 ′ 2
)
⟨1, 2, . . . , N |e |1, 2, . . . , N ⟩ = exp − |r1 − r2 | + . . . |rN − rN |
2πβℏ2 2βℏ2

From this expression its easy to calculate the diagonal elements, because for diagonal elements we have
ri = ri′ . This makes the exponential identically equal to zero and we get the matrix element
( ) 3N
−βH m 2
⟨1, 2, . . . , N |e |1, 2, . . . , N ⟩ =
2πβℏ2

Using the wavelength parameter

√
m
λ=
2πβℏ2

we get the Matrix element as

( )3N
−βH 1
⟨1, 2, . . . , N |e |1, 2, . . . , N ⟩ =
λ

Now the cannonical partition function is just the trace of this expression
∫ ( )3N ( )N
−βH 1 3N V
QN (T, V ) = Tr(e )= d r=
λ λ3

This expression has neigher the gibbs correction factor 1

N! nor the spatial correction factor. □

3. Determine the values of the degeneracy discriminant nλ3 for hydrogen, helium and oxygen at NTP.
Make an estimate of the respectivey temperature ranges where the magnitues of this quantity becomes
coparamble to unity and hence quantum effects become important.
Solution:
The quantity nλ3 can be written in terms of temperature and boltzman constant as

nh3 N h3 h3 P
nλ3 = = = (1)
(2πmkT )3/2 V (2πmkT )3/2 (2πm)3/2 (kT )5/2

For standard temperature and pressure

T = 293KandP = 1.01 × 105

2
 Using the mass of Hiydrogen, Helium and Oxygen we get
6.63 × 10−34 1.01 × 105
H2 : nλ3 = = 2.86 × 10−5
2π(1.67 × 10−27 )3/2 (1.38 × 10−23 × 293)5/2
6.63 × 10−34 1.01 × 105
He2 : nλ3 = = 3.61 × 10−6
2π(6.64 × 10−27 )3/2 (1.38 × 10−23 × 293)5/2
6.63 × 10−34 1.01 × 105
O2 : nλ3 = = 4.78 × 10−7
2π(25.6 × 10−27 )3/2 (1.38 × 10−23 × 293)5/2

INverting the relation (1) and setting nλ3 ≃ 1 we get

( )1/5
1 h6 P 2
T =
K (2πm)3
So for the different masses of H2, He2 and O2 we get

H2 : T = 4.46K
He2 : T = 1.95K
O2 : T = 0.868K

This give the temperature in which the discriminant is close to 1. □

4. A system consists of three particles, each of which has three possible quantum states, which energy 0 ,
2E, or 5E respectively. Write out the complete expression of the cannonical partition function Q for this
system:
(a) if the articles obey Maxwells-Boltzman statistics.
Solution:
The single particle cannonical parition function for
∑
Q1 (V, T ) = e−βEn = 1 + e−2β + e−5β
n

1 N
The cannonical partition function for N distinguishable particles is obtained by QN (V, T ) = N! [Q1 (V, T )]
So for three particles we get
1 [ ]3
Q3 (V, T ) = 1 + e−2β + e−5β
3!
The free energy of the system is
( )
1[ ]3 ( )
F = kT ln Q = kT ln 1 + e−2βE + e−5βE = −kT ln 6 + 3kT ln 1 + e−2βE + e−5βE
6
The entropy is given by
( )
∂F
S=−
∂T N,V
( ) (
2E
6Ee− T k
5E
15Ee− T k
)3 
− Tk
Tk + + e− T k
2E 5E
T 2k T 2k
 1+e 
= + k ln  
1 + e− T k + e− T k
2E 5E
6

This gives the expression for the entropy of the particles. □

(b) if they obey Bose-Einstein statistics,

Solution:
For bose einstein case, the particle sare counted indistinguishable. So each of the three particle can
belong to following energy state So the total partition function of the system becomes

3
 n0,n1,n2 5,0,2 5,5,2 5,5,0 5,2,2 0,2,2 5,0,0 0,2,0 5,5,5 2,2,2 0,0,0
Total Energy 7E 12E 10E 9E 4E 5E 2E 15 E 6E 0

QN (T, V ) = 1 + e−2Eβ + e−4Eβ + e−5Eβ + e−6Eβ + e−7Eβ + e−9Eβ + e−10Eβ + e−12Eβ + e−15Eβ

Similarly the free energy is given by F = kT ln QN (V, T ) and the entropy is given by S = − ∂F
∂T
This gives the expression for the entropy of the particles. □

(c) if they obey Fermi-Dirac statistics,

Solution:
For the particle satisfying Fermi-Dirac statistics no two particles can occupy the same energy levels
so each has to sit on its own energy leven which gives the partition function
[ ]
QN (V, T ) = 1 + e−2βE + e−5βE

The free energy of the system is

( )
F = T k log 1 + e− T k + e− T k
2E 5E

So the entropy becomes

( )
∂F E 2e3Eβ + 5 ( )
S=− =− 5Eβ 3Eβ
− k log 1 + e−2Eβ + e−5Eβ
∂T T (e +e + 1)

This gives the entropy of particles for Fermi-Dirac statistics. □