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HOMEWORK #4 & SOLUTIONS

Problem 1 (Pathria 3.5)

Solution

F (T, V, N ) = Nf (v, T )

v = V/N

N N = N(f + N f

∂v

∂F

V

N 2

V V = V N f

∂F

1

∂v N

)

Adding these two gives the desired equation.

1

Problem 2 The Einstein solid picture assumes that atom i of a solid sits at lattice position

r 0i and can oscillate harmonically around this position. It is described by the Hamiltonian

H =

N

i=1

p

2

i

1

2

2m +

2

N

i=1

(r i r 0i ) 2

(1)

(a) What shape does the phase space volume with energy less than E, i.e., the volume

H(r, p) E have?

(b) Calculate the entropy S of the Einstein solid at a given energy E using classical theory.

Note, the oscillators have diﬀerent origins and thus the atoms are distinguishable!

Solution

 (a) H(r, p) ≤ E deﬁnes a 6N dimensional ellipsoid. Axis lengths are √ 2mE and 2E/mω 2 . (b) Use x i = mω(r i − r i0 ). For distinguishable particles:

Σ(E) =

h 3N P

1

3N

2

i=1 (p i

+x

)E d 3N pd 3N q
2
i

This is the volume of a 6N dimensional sphere of radius 2mE:

Σ(E) =

1

π

3N

Γ(3N ) (2mE) 3N =

hmω 3N 3N

3N Γ(3N )

1

ω 3N

E

By diﬀerentiation with respect the energy

By using

g(E, V, N) =

1

E 3N1

ω 3N Γ(3N )

Ω = gE and ln(Γ(3N )) = ln((3N 1)!) N ln(N ) N

S(E, V, N) = 3Nk 1 + ln(

ω )

E

N

Classical oscillators with quantum result!

2

(2)

(3)

(4)

(5)

Problem 3 A simple model for a polymer in two dimensions is that of a path on a square

lattice. At every lattice point the polymer can either go straight or choose between the two

directions in a right angle with respect to its current direction. Each time it bends in a

right angle, it pays a bending energy . Thus, for a given shape of the polymer the total

bending energy of the polymer is times the number of right angle turns. We assume that

the starting segment of the polymer is ﬁxed somewhere on the lattice and that the polymer

consists of N + 1 segments. Each possible shape of the polymer is a state of this statistical

mechanics system.

(a) How many polymer shapes have a total bending energy E where we assume E = m

with some integer 0 m N ? (Hint: First count how many ways there are to position

the m right angles on the polymer of length N + 1 segments and then take into account that

there are 2 possible choices for each right angle, namely left and right.)

(b) What is the entropy S(E, N ) of this system? Approximate all factorials with the help

of Stirling’s formula.

(c) Calculate the temperature of this system as a function of the total bending energy E

and the length N of the polymer.

(d) Calculate the energy E of the polymer as a function of the temperature T and of the

length N of the polymer.

(e) Calculate the heat capacity at constant length C N as a function of the temperature T

and the length N of the polymer.

Solution

(a) There are m right angle turns and N m straight steps. There are

N!

(N m)!m!

(6)

ways to arrange the turns. Each right angle turn can go into two directions, so the number

of polymer shapes are

(7)

N!

N(E) =

(N

m)!m! 2 m

(b) Using Stirling:

S = kln(N (E)) = kN m

N ln(2) m

N ln( m

N ) (1 m

N )ln(1 m

N )

(8)

3

(c)

Remembering that m = E/ :

1

T

=

∂S

E N = k ln(2) ln( m

N ) + ln(1 m

N )

(9)

(d) From the result derived in (c), using β = 1/kT

that is

(f)

e β = 2 2

E

N

E

N

E

=

2N 2 + e

β

,

C N = E ∂T

N

 = Nk(β ) 2 4

2e

β

(2 +

e β ) 2

(10)

(11)

(12)