1 Problem 9.

23
Which configuration has a greater number of unpaired spins? Which one has
a lower energy? [Kr]4d9 5s1 or [Kr]4d10 . What is the element and how does
Hund’s rule apply?

1.1 Solution
The element is Pd. The configuration [Kr]4d10 has a lower energy, but a higher
number of unpaired spins. This is due to filled subshells having a lower energy.
This is one of the cases where Hund’s rule is violated.

2 Problem 9.24
The answer (except for Z = 19) can be seen in Figure 1. All credit to McGraw-
Hill for the image.

Figure 1: The spin configurations for Z = 11 through Z = 18. All credit to

McGraw-Hill for the image

For Z = 19, the additional electron will occupy the 4s subshell, giving a
condensed configuration of [Ar]4s1 . The image will look just like before, but
now there’s a 4s block on the right with one arrow in it.

3 Problem 9.25
What is the average temperature of plasma, which is formed by ionized atoms?

1
3.1 Solution
Here we actually use a result from stat mech, that for a monatomic gas
3
K̄ = kT
2
Where k is Boltzmann’s constant. For the atoms to be ionized, the average
temperature must be on the order such that they have enough energy for the
electrons to constantly be getting kicked loose. We see that the typical ionization
energy is ≈ 5 eV. Since Boltzmann’s constant is ≈ 10−5 eV, we see that we must
have a temperature of T ≈ 105 K.

4 Exercise 10.1
(a) Show that
2πN E
n(E)dE = 3/2
E 1/2 e− kT dE
V (πkT )
(b) Show that
3 N kT
Ē =
2 V

4.1 Solution
4.1.1 Part (a)
Start with the Maxwell-Boltzmann distribution for velocity:

4πN  m 3/2 2 − mv2

n(v)dv = v e 2kT dv
V 2πkT
Remember that for kinetic energy, we have
1
E= mv 2
2
Taking the derivative of both sides gives
dE 1
= mv → dE = dv
dv mv
Plugging these in gives

4πN  m 3/2 v − E
n(E, v)dE = e kT dE
V 2πkT m
To get rid of that remaining v we rearrange the definition of kinetic energy
to get

2
 r
2E
v=
m
Plugging this in gives
r
4πN  m 3/2 2E − E
n(E)dE = e kT dE
V 2πkT m3
The m’s cancel out. If we cancel out some of the 2’s as well, we will get
2πN E
n(E)dE = E 1/2 e− kT dE
V (πkT )3/2
as needed.

4.1.2 Part (b)

In this section, we use
Z ∞
Ē = En(E)dE
0
Which becomes
Z ∞
2πN E
Ē = E 3/2 e− kT dE
V (πkT )3/2 0

Solving the integral gives

2πN 3√
Ē = 3/2
(kT )5/2 πdE
V (πkT ) 4
This just simplifies to
3 N kT
Ē =
2 V
as needed.

5 Problem 10.2
Show that the most probable speed for a particle in a Maxwell-Boltzmann dis-
tribution is
r
2kT
vmp =
m

3
5.1 Solution
In the Maxwell-Boltzmann distribution, the likelihood of finding a particle with
a particular velocity v (per unit volume) is given by

4πN  m 3/2 2 − mv2

n(v)dv = v e 2kT dv
V 2πkT
The way to maximize any function is to find where its derivative is 0.
d
n(v) = 0
dv
Throwing out the constants out front, this turns into
d 2 − mv2
0= v e 2kT
dv
Make sure to remember the chain rule
mv 2
 m  mv2
0 = 2ve− 2kT + v 2 − 2v e− 2kT
2kT
Canceling some terms out gives
m
1 = v2
2kT
Solving for v (and only keeping the positive root, a negative speed makes no
sense) gives
r
2kT
vmp =
m

6 Problem 10.7
A molecule with a dipole moment p~ is placed in an external electric field, ~. The
molecule can only be parallel or antiparallel to the field.
(a) Show that there are two allowed energy states separated by 2p.
(b) Let the ground state have energy 0. The fraction of degeneracies between
the excited and ground states is 2. If there are N particles at temperature T ,
what is the ratio of particle sin the excited state to the ground state?
(c) Find the temperature for which this ratio is 1.9. Estimate p ≈ 10−30 C·m
and  ≈ 106 V/m.
(d) Calculate Ē for some temperature T . Show that Ē → 0 as T → 0 and
4p
Ē → as T → ∞
3
(e) What is Etotal ? Show that the heat capacity is
  2  
Nk 2p exp[2p/kT ]
C=
2 kT (1 + 0.5 exp[2p/kT ])2
(f) Sketch C. Where is it maximized? Explain the relationship in physical
terms.

4
6.1 Solution
6.1.1 Part (a)
We know that there are only two states because there are only two allowed
orientations of the molecule: parallel and anti parallel. The energy of these
states is given by

E = −~
p · ~
We can see that

Eparallel = −p and Eantiparallel = p

So their difference will be

∆E = 2p

6.1.2 Part (b)

The ratio of molecules in the excited state to the ground state is defined as

g(2p)PM B (2p)
R=
g(0)PM B (0)
The probability that a state is occupied is given by
E
PM B (E) = Ae− kT
The constant out front will cancel out when we take the ratio. Also e0 = 1
giving

R = 2e−2p/kT

6.1.3 Part (c)

Solving for T gives
 
2p R
T =− ln
k 2
Plugging in the given values yields

2(10−30 )(106 )
 
1.9
T =− ln ≈ 2.82K
1.4 × 10−23 2

5
6.1.4 Part (d)
Since we are working with a two level system, we cannot use the integral def-
inition of average. We must instead use the discrete definition. Since we are
dealing with a Maxwell-Boltzmann distribution, the probability that a particle
will be found in a state with energy Ei is
Ei
P (Ei ) = Ae− kT
We still have the normalization condition that
X
1= g(Ei )P (Ei )
i

Notice that we are careful to include degeneracy. In our case, this reduces
to

1 = Ae0 + 2Ae−2p/kT
We can use this to solve for A, giving
1
A=
1+ 2e−2p/kT
Now we can use the discrete definition of average to get our answer
X
Ē = g(Ei )P (Ei )Ei
i

In our case we have

Ē = AE 0 (0) + A(4p)e−2p/kT
This becomes

(4p)e−2p/kT
Ē =
1 + 2e−2p/kT
Dividing the top and bottom by 2e−2p/kT gives
2p
Ē = 1 2p/kT
1+ 2e

If we let T → 0, then the denominator erupts, and we get Ē = 0.

On the other hand, if we let T → ∞, then the exponential goes to 1. From
4
here it’s just a little algebra to get Ē = p.
3

6
6.1.5 Part (e)
First we have

Etotal = N Ē
Then we have
d
C= Etotal
dT
Now the fun begins. Make sure to be careful with the chain rule!
d 2p
C= N
dT 1 + 12 e2p/kT
  
(−1) 1 2p/kT 2p −2
C = N 2p
2 e (−T )
1 + 21 e2p/kT 2 k
Rearranging this around a bit, we can get the answer from the book
2
e2p/kT

Nk 2p
C=
2
2 kT 1 + 12 e2p/kT

6.1.6 Part (f )
Let’s let
2p
z=
kT
This makes

Nk z 2 ez
C(z) =
2 1 + 1 ez 2


2
From here, there are two ways to proceed. You can find the maximum the
hard way, by using the chain rule, or by graphing the function. Let’s choose
the later. Wolfram Alpha plotted the function and tells us that the maximum
value is at 2.65.

7 Problem 10.8
Use the result from Exercise 10.1
2πN E
n(E)dE = E 1/2 e− kT dE
V (πkT )3/2
Find:
(a) the most probable energy
(b) the average energy
(c) the rms energy.

7
 Figure 2: Plot of C(z) done by Wolfram Alpha

7.1 Solution
7.1.1 Part (a)
The way to maximize any function is to find where its derivative is 0.
d
n(E) = 0
dE
We can throw away the constants out front to get
d 1/2 − E
E e kT = 0
dE
Using the chain rule, we get
 
1 −1/2 − E 1 E
E e kT +E 1/2
− e− kT = 0
2 kT
Canceling out the exponential, consolidating the E terms gives
2Emp
1=
kT
Solving for Emp gives
kT
Emp =
2

7.2 Part (b)

The average energy is given by
Z ∞
V
Ē = En(E)dE
N 0

8
 Or
Z ∞
V 2πN E
Ē = E 3/2 e− kT dE
N V (πkT )3/2 0

Solving the integral gives

2π 3√
Ē = 3/2
(kT )5/2 πdE
(πkT ) 4
Simplifying
3
Ē =
kT
2
This is essentially the same problem as Exercise 10.1 Part (b). I apologize
for the redundancy. At least you could have just copied your own work.

7.3 Part (c)

To find the rms energy, we must first find the average of the square of the energy
Z ∞
V
E¯2 = E 2 n(E)dE
N 0
Or
Z ∞
V 2πN E
E¯2 = E 5/2 e− kT dE
N V (πkT )3/2 0

Solving the integral gives

2π 15 √
E¯2 = 3/2
(kT )7/2 π
(πkT ) 8
Simplifying gives
15
E¯2 = (kT )2
4
This means that our Erms will be
r
15
Erms = kT
4

8 Problem 10.12
Calculate the average photon energy in a Bose-Einstein gas at
(a) Temperature T
(b) T = 6000K

9
8.1 Solution
For a Bose-Einstein gas, we have

8πE 2 1
n(E)dE = dE
(hc)3 eE/kT − 1
The average energy per photon is given by
R∞
En(E)dE
Ē = R0 ∞
0
n(E)dE
If we plug in n(E)dE we will see that all of the messy constants cancel out
R∞ 3 1
E E/kT dE
Ē = R ∞ 2 e 1 −1
0

0
E eE/kT −1 dE
E
If we let z = , then we also have E = kT z and dE = kT dz. Plugging
kT
these in gives
R∞
(kT )4 0 z 3 ez1−1 dz
Ē = R∞
(kT )3 0 z 2 ez1−1 dz
Plugging in the formulae in the book gives

π 4 kT
Ē =
15 × 2.41

8.2 Part (b)

Here we use T = 6, 000 K and k = 8.6 × 10−5 eV/K

π 4 (8.6 × 10−5 × 6000

Ē = ≈ 1.4eV
15 × 2.41
This actually fits in well with our calculation of ionization energies of plasma
in Problem 9.25. These photons aren’t hot enough to ionize gasses, but they’re
not too far off (Eion ≈ 5eV) and we predicted an ionization temperature of
≈ 105 K.

9 Problem 10.16
3
Show that the average kinetic energy in a Fermi gas is Ē EF .
5

10
9.1 Solution
For a Fermi gas we have
√ 3/2
8 2πme E 1/2 1
n(E)dE = dE
h3 e(E−EF )/kT + 1
The average energy per electron is given by
R∞
En(E)dE
Ē = R0 ∞
0
n(E)dE
If we plug in n(E)dE we will see that all of the messy constants cancel out
R ∞ 3/2 1
0
E (E−EF )/kT +1 dE
Ē = R ∞ 1/2 e
0
E e(E−EF1)/kT +1 dE
Now we must remember that at 0 K, the Fermi Dirac distribution goes to
zero for energies above the Fermi energy. It goes to 1 for energies below the
Fermi energy.
R EF
E 3/2 dE
Ē = R0EF
0
E 1/2 dE
Neither of these integrals is too tricky. They work out so that
2 5/2
5 EF
Ē =
2 3/2
3 EF
Or simplifying
3
Ē = EF
5

10 Problem 10.19
Calculate the probability that an electron in Cu at 300 K has an energy equal
to 99% of the Fermi energy.

10.1 Solution
For a Fermi gas we have
1
PF D (E)dE = dE
e(E−EF )/kT + 1
We are curious about Ec = .99EF , so
1
PF D (Ec )dE = dE
e−0.01EF /kT + 1

11
 Plugging in EF = 7.05 eV for Cu, T = 300K, and k = 8.6 × 10−5 eV/K, we
will get
1
PF D (Ec )dE = dE ≈ 0.94
e−0.01(7.05)/(300×8.6×10−5 ) + 1
So it is very likely that this energy will be filled.

11 Additional Problem 1
11.1 Solution
See Figure 3 for the solution. There are 24 = 16 possible outcomes.There
are 4 + 1 = 5 macrostates. The macrostates are divided up using lines. The
probabilities of each macrostate are in the rightmost column. The multiplicity
of the macrostate can be gotten by multiplying the probability by 16.
The equation for checking each macrostate is
N!
Ω(n) =
n!(N − n)!
For each of the cases these are
4! 4!
Ω(0) = = =1
0!(4 − 0)! 0!4!
4! 4!
Ω(1) = = =4
1!(4 − 1)! 1!3!
4! 4!
Ω(2) = = =6
2!(4 − 2)! 2!2!
4! 4!
Ω(3) = = =4
3!(4 − 3)! 3!1!
4! 4!
Ω(4) = = =1
4!(4 − 4)! 4!0!
Yes, these numbers agree.

12 Additional Problem 2
12.1 Solution
12.1.1 Part (a)
There are 250 ≈ 1.126 × 1015 possible outcomes.

12
Figure 3: The possible outcomes from tossing 4 coins. Credit to B. Wagner for
making the table

12.1.2 Part (b)

We using the multiplicity formula again
N!
Ω(n) =
n!(N − n)!
In our case
50!
Ω(25) = ≈ 1.26 × 1014
25!25!

12.1.3 Part (c)

The probability of getting n heads is given by

13
 Ω(n)
P (n) =
Ω(all)
So for us it will work out to be
50!
P (25) = ≈ 0.112
25!25! · 250

12.1.4 Part (d)

The multiplicity of getting 30 heads is
50!
Ω(30) =
30!(20)!
This means the probability of getting 30 heads is
50!
P (30) = ≈ 0.0419
30!(20)! · 250

12.1.5 Part (e)

The multiplicity of getting 40 heads is
50!
Ω(40) =
40!(10)!
This means the probability of getting 40 heads is
50!
P (40) = ≈ 9.12 × 10−6
40!(10)! · 250

12.1.6 Part (f )
The multiplicity of getting 50 heads is
50!
Ω(50) = =1
50!0!
This means the probability of getting 40 heads is
1
P (50) = ≈ 8.88 × 10−16
250
This is only from flipping 50 coins, and there is already a difference in 15
orders of magnitude between the most and least likely state. Imagine how sharp
this gets when you have 1023 coins (i.e. particles)!

14
13 Addition Problem 3
13.1 Solution
This one you can just plug into your favorite calculator. The point is to just
1.4
give you a sense of scale. It works out so that x ≈ 1010 ≈ 1010,000,000,000 .
That’s insanely huge!

15