Homework #6 Solutions

1. Chap.4: prob. 3 - The partition function is

Z = ∑ exp(− Ei / k BT ) = e0 + e −1 + e−1 + e−1 + e−2 + e −2 + e−2 + e−2 + e−2 = 2.7803 .
allstates ,i
The probability of: i) the low energy state is e0/2.7803 = 0.3597, ii) one of the second energy states is e-1/2.7803 =
0.1323, and iii) one of the highest energy states is e-2/2.7803 = 0.0487. So the total probability of finding the
system with energy 100kB is 0.3969 and the total probability of finding the system with energy 200kB is 0.2434.
B B

The average energy is 0 + 100kB(0.3969) + 200kB(0.2434) = 88.37kB.

B B B

2. Chap. 4: prob. 4 a) -
∂ ⎛ ∑ exp( − βε i ) ⎞⎟
⎛ ∂ ln( Z ) ⎞ 1 ∂Z 1 ⎜⎝ i ⎠ = − 1 ∑ ∂ ( exp(− βε i ) ) = ∑ ε i exp(− βε ) = ∑ ε P = U .
−⎜ ⎟ =− =−
⎝ ∂β ⎠ Z ∂β ∂β ∂β
i i i
Z Z i i Z i

b) First, we have to notice that <(E - <E>)2> = <(E2 - 2E<E> + <E>2)> but the averaging can be done on
the three terms separately so that <(E - <E>)2> = <E2> - 2<E><E> + <E>2 = <E2> - <E>2. This is the
relation that we should show comes from the second partial of lnZ.

⎛ ∂ ln( Z ) ⎞
⎜
2
⎟ = −
⎛ ε
⎝i Z
⎞
∂ ⎜ ∑ i exp( − βε i ) ⎟
⎠=−1( i
)
∂ ∑ ε i exp( − βε i )
1 ⎛
+ 2 ⎜ ∑ ε i exp(− βε i ) ⎟
⎞ ∂Z
⎝ ∂β
2
⎠ ∂β Z ∂β Z ⎝ i ⎠ ∂β
−ε i2 1
= −∑ exp(− βε i ) − 2 ∑ ε i exp(− βε i )∑ ε j exp(− βε j ) =< E 2 > − < E > 2 =< ( E − < E > )2 >
i Z Z i j

c) Mean square deviation of the thermal energy is ∂2(lnZ)/∂β 2 = -∂U/∂β = -(∂U/∂T)(dT/dβ) = kBT 2CV.
For your Monte Carlo simulations (where E can vary), this means that a calculation of the mean square
deviation of the total energy, will give you the heat capacity of your system if you know the temperature.

3. Chap. 4: prob. 5 - Generally, you will find that the population of an energy level goes up as the
energy of the level goes down. Eventually, we want to find the contribution of these three energy levels
to the molar specific heat so lets assume that we have one mole of this molecule, i.e. Avogadro’s number
of molecules, N = NA. For a single molecule in thermal contact with the other molecules we know that p3
= exp(-β10ε)/Zone molecule = exp(-β10ε)/[1 + exp(-βε) + exp(-β10ε)] and p2 = exp(-βε)/Zone molecule = exp(-
βε)/[1 + exp(-βε) + exp(-β10ε)]. So the second energy level will be occupied p2/p3 = exp(9βε) times as
often as the highest energy level.
Practically speaking we can probably ignore the highest energy level whenever p2/p3 >> 1 (say p2/p3 > 104
which would mean T < 9ε/kBln(104) ) and I would be satisfied if you gave this answer. However, we
could also argue that the number of molecules in the highest energy state is n3 = NAp3 and that if this is
less than 1 then, since we can’t have less than one molecule in some state, we have to say that the highest
energy state is unoccupied. So we write n3 < 1 and plug in the p3. Doing this shows that e9βε > NA/2 so
that T < 9ε/[kBln(NA/2)] (these two answers only differ by a factor of 6). This shows that whenever the
available thermal energy per degree of freedom, kBT, is less than about 0.2ε then 10ε energy level will be
empty even though there are Avogadro’s number of molecules.
The average energy of one molecule is <E> = 10εp3 + εp2 + 0p1 so just plug in the probability functions
above to find the temperature dependence of <E>.
The energy of one mole is U = NA<E> and CV = ∂U/∂T)V so the molar specific heat is cV = ∂U/∂T)V if our
sample size is one mole. If my math is correct you get
 cV = N A
ε2 (e − ε / k BT
+ 100e −10ε / k BT + 81e −11ε / k BT ).
k BT 2
(1 + e
+e −ε / k B T
)
−10ε / k BT 2
0.5
3-level system
This function is plotted in the figure to the right. The whole
point of this problem was to let you see that the temperature
0.4
dependence of the heat capacity shows you the energy level C
structure. At low T you see quantum effects very strongly. V

Roughly speaking, as T increases, the heat capacity drops 0.3

whenever kBT passes an energy level and increases again as kBT
approaches a new energy level. The heat capacity is really just 0.2
telling you about the density of energy levels per unit energy at
an energy of about kBT. At lowest T only the ground state has a 0.1
significant population. As T is raised, eventually higher and
higher energy states have molecules in them. The heat capacity 0
increases every time new “ways of having energy” are added to 0 2 4 6 8 10 12 14
the system. T

4. Chap. 4: prob. 12 - a) At low T the energy is as low as possible (all atoms in their ground state) and
the total entropy is as small as possible (only one state so zero entropy). This means that K0 = N.
b) At high T the entropy increases as much as it can. Highest T will have the highest entropy state which
is when each of the 10 states is equally occupied. This means that K0 = N/10.
c) You can factor this partition function so consider one ion. Probability of occupation of state i by this
ion is Pi(T) = e-εi/kBT / Z where Z = [1 + e-ε/kBT + e-2ε/kBT + … + e-9ε/kBT]. The low T limit is when ε/kBT <<
1 and in this limit Z → 1 + e-ε/kBT so Pi(T) → e-εi/kBT / (1 + e-ε/kBT) ≅ e-εi/kBT (1 - e-ε/kBT). The total number
of spins in state i = Ki(T) = N Pi(T) ≅ N e-εi/kBT (1 - e-ε/kBT). For i = 0 you get K0(T) = N(1 - e-ε/kBT).
d) For i = 1 you get K1(T) = N e-ε/kBT (1 - e-ε/kBT) down by a factor of e-ε/kBT from K0.
e) In the high T limit ( kBT >> 9ε) you get e-εi/kBT → (1 – εi/kBT) etc. for all εi so Z → 10(1 – 4.5ε/kBT)
and K0(T) → (N/10)(1 + 4.5ε/kBT) which increases (from N/10) as T decreases.