Statistical Physics: September 12, 2012

Solution for the Homework 1

Problem 6.5: Imagine a particle that can be in only three states, with energies -0.05eV, 0 and 0.05eV.
This particle is in equilibrium with a reservoir at 300K.
(a) Calculate the partition function for this particle.
Solution:

Z1 = eE(s)/kT = e+0.05/300k + 1 + e0.05/300k (1)
s

(b) Calculate the probability for this particle to be in each of the three states.
Solution:
+0.05/300k
e /Z1 if the energy of state is -0.05eV
E(s)/kT
P (s) = e /Z1 = 1/Z1 if the energy of state is 0 (2)
0.05/300k
e /Z1 if the energy of state is +0.05eV

(c) Because the zero point for measuring energies is arbitrary, we could just as well say that the
energies of the three states are 0, +0.05eV, and +0.10eV, respectively. Repeat parts (a) and (b)
using these numbers. Explain what changes and what doesnt.
Solution:

Z2 = eE(s)/kT = 1 + e0.05/300k + e0.10/300k (3)
s
( )
= e0.05/300k e+0.05/300k + 1 + e0.05/300k = Z1 e0.05/300k (4)

Similarly to the above,

1/Z2 if the energy of state is 0
P (s) = eE(s)/kT /Z2 = e0.05/300k /Z2 if the energy of state is +0.05eV (5)
0.10/300k
e /Z2 if the energy of state is +0.10eV
+0.05/300k
e /Z1 if the energy of state is 0
= 1/Z1 if the energy of state is +0.05eV (6)
0.05/300k
e /Z1 if the energy of state is +0.10eV

The energies of the three states just moved with same dierences of energies. It changes the
partition function, but the probability for some particle to be in each of the three states are not
changed.

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 Statistical Physics: September 12, 2012

Problem 6.10: A water molecule can vibrate in various ways, but the easiest type of vibration to
excite is the exing mode in which the hydrogen atoms move toward and away from each other
nut the HO bonds do net stretch. The oscillations of this mode are approximately harmonic,
with a frequency of 4.8 1013 Hz. As for any quantum harmonic oscillator, the energy levels are
1 3 5
2 hf, 2 hf, 2 hf , and so on. None of these levels are degenerate.
(a) Calculate the probability of a water molecule being in its exing ground state and in each of
the rst two exited states, assuming that it is in equilibrium with a reservoir (say the atmosphere)
at 300 K. (Hint: Calculate Z by adding up the rst few Boltzmann factors, until the rest are
negligible.)
Solution:

Z = eE(s)/kT = ehf /2kT + e3hf /2kT + e5hf /2kT + 2.15166 102 (7)
s

Using this partition function, we can calculate some particle to be in the rst three energy states.

P (s = 0) = eE(s=0)/kT /Z = ehf /2kT /Z 9.99537 101 (8)

E(s=1)/kT 3hf /2kT 4
P (s = 1) = e /Z = e /Z 4.62323 10 (9)
E(s=2)/kT 5hf /2kT 7
P (s = 2) = e /Z = e /Z 2.13842 10 (10)

(b) Repeat the calculation for a water molecule in equilibrium with a reservoir at 700 K (perhaps
in a steam turbine).
Solution:

P (s = 0) 9.6278 101
Z 2.00383 101 P (s = 1) 3.58347 102 (11)

P (s = 2) 1.33377 103

Problem 6.12: Cold interstellar molecular clouds often contain the molecule cyanogen (CN), whose
rst rotational exited states have an energy of 4.7 104 eV (above the ground state). There are
actually three such excited states, all with the same energy. In 1941, studies of the absorption
spectrum of starlight that passes through these molecular clouds showed that for every ten CN
molecules that are in the ground state, approximately three others are in the three rst exited
states (that is, an average of one in each of three states). To account for this date, astronomers
suggested that the molecules might be in thermal equilibrium with some reservoir with a
well-dened temperature. What is that temperature?
Solution: From the observation data, we know the ratio of probabilities of ground state and
rst excited states. There are three rst excited states and so we need to divide the ratio by
three. Then, using the given energy dierence, we can get the result.

P (s = 1) 4 eV /kT 1
= e(E(s=1)E(s=0))/kT = e4.710 (12)
P (s = 0) 10
4.7 104
T = 2.3687K (13)
ln(10) k

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 Statistical Physics: September 12, 2012

Problem 6.18: Prove that, for any system in equilibrium with a reservoir at temperature T, the
average value of E 2 is
1 2Z
E2 = . (14)
Z 2
Then use this result and the results of the previous two problems to derive a formula for E in
terms of the heat capacity, C = E/T . You should nd

E = kT C/k (15)

Solution: Consider the partition function Z = s eE(s) and let us calculate the right-hand
side of given equation.
( ) ( )
1 2Z 1 E(s) 1 2 E(s)
= [E(s)]e = E(s) e E2 (16)
Z 2 Z s
Z s

Similarly, we can get the average value of arbitrary power of E by dierentiating the partition
function several times. Use this result and the average value of E, we can nd the expressions
of standard deviation of E in terms of heat capacity.
( ) ( )
2 1 2Z 1 Z 2 1 2Z 1 Z
2
E = E2 E = = + (17)
Z 2 Z 2 Z 2 Z
( )
1 Z E T E
= = = = kT 2 C (18)
Z T
So, take square root to get the given result.

C
E = kT (19)
k

Problem 6.20: This problem concerns a collection of N identical harmonic oscillators (perhaps an
Einstein solid or the internal vibrations of gas molecules) at temperature T. As in Section 2.2,
the allowed energies of each oscillator are 0, hf , 2hf , and so on.
(a) Prove by long division that
1
= 1 + x + x2 + x3 + . (20)
1x
For what values of x does this series have a nite sum?
Solution: Divide 1 by (1 x), then you can easily get the result. But the result is innite series.
We want to make this series converge, so the magnitude of x should less than 1, i.e. |x| < 1.
(b) Evaluate the partition function for a single harmonic oscillator. Use the result of part (a) to
simplify your answer as much as possible.
Solution:
1
Z = eE(s) = 1 + ehf + e2hf + = (21)
s
1 ehf

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 Statistical Physics: September 12, 2012

(c) Use formula 6.25 to nd an expression for the average energy of a single oscillator at tem-
perature T. Simplify your answer as much as possible.
Solution:
( )
1 Z 1 1 ehf hf
E = = = hf = hf (22)
Z Z 1 ehf 1e hf e 1

(d) What is the total energy of the system of N oscillators at temperature T? Your result should
agree with what you found in Problem 3.25.
Solution: Let the total energy is U. Then,
N hf
U = NE = (23)
ehf 1

(e) If you havent already done so in Problem 3.25, compute the heat capacity of this system
and check that it has the expected limits as T 0 and T .
Solution: Take the derivative of temperature to the total energy.
( )
U hf 1 N h2 f 2 ehf N h2 f 2 ehf
C = = = = (24)
T T ehf 1 kT 2 (ehf 1)2 kT 2 (ehf 1)2

Now, take a limit for the temperature.

N h2 f 2 ehf N h2 f 2 1
T 0, 0 (25)
kT 2 (ehf 1)2 kT 2 ehf /kT
N h2 f 2 ehf N h2 f 2 1 + hf /kT
T , Nk (26)
2
kT (e hf 1) 2 kT 2 (1 + hf /kT 1)2

Problem 6.22: In most paramagnetic materials, the individual magnetic particles have more than
two independent states (orientations). The number of independent states depends on the par-
ticles angular momentum quantum number j, which must be a multiple of 1/2. For j = 1/2
there are just two independent states, as discussed in the text above and in Section 3.3. More
generally, the allowed values of the z component of a particles magnetic moment are

z = j , (j + 1) , , (j 1) , j , (27)

where is a constant, equal to the dierence in z between one state and the next. (When
the particles angular momentum comes entirely from electron spins, equals twice the Bohr
magneton. When orbital angular momentum also contributes, is somewhat dierent but
comparable in magnitude. For an atomic nucleus, is roughly a thousand times smaller.) Thus
the number of states is 2j + 1. In the presence of a magnetic eld B pointing in the z direction,
the particles magnetic energy (neglecting interactions between dipoles) is z B.
(a) Prove the following identity for the sum of a nite geometric series:

1 xn+1
1 + x + x2 + + xn = . (28)
1x

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 Statistical Physics: September 12, 2012

(Hint: Either prove this formula by induction on n, or write the series as a dierence between
two innite series and use the result of Problem 6.20(a).)
Solution: For n = 1, given identity is simply true.

1 x2
1+x = (29)
1x
Let us suppose that the identity is satised for n = k 1 case. Then,

1 xk 1 xk xk xk+1 1 xk+1
1 + x + + xk1 + xk = + xk = + = (30)
1x 1x 1x 1x
By the mathematical induction, the relation is true.
(b) Show that the partition function of a single magnetic particle is

sinh [b (j + 1/2)]
Z= , (31)
sinh b/2
where b = B.
Solution: The energy states are discrete because of the magnetic moments of particles are
discrete.

j
z B
Z = e = ei B (32)
s i=j
( )
= ejb + e(j+1)b + + ejb = ejb 1 + eb + + e2jb (33)
ejb e(j+1)b e(j+1/2) e(j+1/2)b sinh [b (j + 1/2)]
= = = (34)
1e b e b/2 e b/2 sinh b/2

(c) Show that the total magnetization of a system of N such particles is

[( ) [ ( )] ]
1 1 1 b
M = N j + coth b j + coth , (35)
2 2 2 2

where coth x is the hyperbolic cotangent, equal to cosh x/ sinh x. Plot the quantity M/N vs.
b, for a few dierent values of j.
Solution: Using the similar trick with the average of energy,
( )
N Z N sinh [b (j + 1/2)]
M = N z = = (36)
BZ BZ sinh b/2
( )
N b sinh [b (j + 1/2)]
= (37)
BZ b sinh b/2
[( ) ( ) ]
N 1 cosh [b (j + 1/2)] 1 b sinh [b (j + 1/2)]
= B j + coth (38)
BZ 2 sinh b/2 2 2 sinh b/2
[( ) [ ( )] ]
1 1 1 b
= N j + coth b j + coth (39)
2 2 2 2

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 Statistical Physics: September 12, 2012

b
-3 -2 -1 1 2 3
j=1 2
-2 j=3 2
j=5 2

-4 j=7 2
j=9 2

(d) Show that the magnetization has the expected behavior as T 0.

Solution: If T 0, then b and so coth b 1.
[( ) [ ( )] ]
1 1 1 b
T 0, M = N j + coth b j + coth (40)
2 2 2 2
[ ]
1 1
N j + = jN (41)
2 2

(e) Show that the magnetization is proportional to 1/T (Curies law) in the limit T . (Hint:
First show that coth x 1/x + x/3 when x 1.)
Solution: Show the hint rst.
ex + ex
x 1, coth x = (42)
ex ex
(1 + x + x2 /2) + (1 + x + x2 /2)
= (43)
(1 + x + x2 /2 + x3 /6) (1 + x + x2 /2 + x3 /6)
( )1
2 + x2 2 + x2 x2
= = 1+ (44)
2x + x3 /3 2x 6
( )( 2
)
1 x x
+ 1 (45)
x 2 6
1 x x 1 x
+ = + (46)
x 2 6 x 3

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 Statistical Physics: September 12, 2012

Since T , b 0 and so coth b follows the hint. So,

[( ) [ ( )] ]
1 1 1 b
T , M = N j + coth b j + coth (47)
2 2 2 2
[( )( 
( )) ( )]
1 1  b 1 1 2 b
N j +  + j+  + (48)
2  +
b(j 1/2) 3 2 2 b 6
[ ( ) ]
1 1 2 1
= N b j+ (49)
3 2 12

Result is proportional to b and so the magnetization is proportional to 1/T in the limit T .

(f) Show that for j = 1/2, the result of part (c) reduces to the formula derived in the text for a
two-state paramagnet.
Solution: Let j = 1/2. Then,
[ ]
1 b
M = N coth b coth (50)
2 2
[ ]
eb + eb eb/2 + eb/2
= N b (51)
e eb 2(eb/2 eb/2 )
[ ]
2(eb + eb ) (eb/2 + eb/2 )2
= N (52)
2(eb/2 + eb/2 )(eb/2 eb/2 )
[ ] ( )
(eb/2 eb/2 )
2 1 b
= N (( = N tanh (53)
2(eb/2 + eb/2 )(
(e(b/2((e(
b/2 ) 2 2

This result exactly follows the formula derived in the text for a two-state paramagnet.