Homework 1 (13 points total) PHY 392K

Due 2/2/12 Solutions by Dan Birt, danbirt@gmail.com

Problem 1 (1 point)
Kittel Chapt. 1-1: Use vector analysis to find the angle between the bonds of diamond. They
are tetrahedral bonds.

Ÿ Solution

Let the carbon at the vertex have coordinates {0,0,0} and side of the cubic lattice have length 2.
Then the coordinates of the other two carbons froming the angle are {1,1,1} and {1,-1,-1}. The
v ×v
angle Θ between two vectors satisfies cosHΘL = ¤ v 1¤¤ v2 ¤ .
1 2

v1 = 81, 1, 1<;
v2 = 81, - 1, - 1<;
ArcCos@v1.v2  HNorm@v1D * Norm@v2DLD * 180  Π  N
109.471

The angle between the bonds of diamond is 109.47°.

Problem 2 (1 point)
Kittel Chapt. 1-2: Consider the planes with indices (100) and (001) referenced to a
conventional cubic cell. What are the indices referenced to the primitive axes shown in Fig. 11?

Ÿ Solution

The primitive axes shown in the figure can be written as vectors a1={1,1,0}, a2={0,1,1},
a3={1,0,1} in the 8x, y, z< basis. Following the rules in Kittel, we note that the vectors a1 and a3
intersect the (100) plane and their lengths will have a 1:1 ratio at the points of intersection.
Therefore, (100) in the 8x, y, z< basis becomes (101) in the 8a1, a2, a3< basis. Similarly,
vectors a2 and a3 intersect the (001) plane and their lengths also have a 1:1 ratio at the points of
intersection. So, (001) in the 8x, y, z< basis becomes (011) in the 8a1, a2, a3< basis.

Problem 3 (2 points)
2 homework1.nb

Problem 3 (2 points)
Kittel Chapt. 2-5: Consider the conventional cube cell for diamond. (a) Determine the structure
factor of this basis. (b) Find the zeros of the structure factor and show that the allowed
reflections satisfy v1 + v2 + v3 = 4 n where all indices are even and n is an integer, otherwise all
indices are odd.

Ÿ Solution

The structure factor is defined as SG = Új f j expH-ä G × r jL, which is a discrete Fourier transform
of the atomic form factors f j. The diamond structure can be thought of as two fcc crystals offset
by the basis{1/4,1/4,1/4} in units of the fcc lattice constant. Note that
SG total = SG fcc 1 + SG fcc 2
= â f j exp H-äG × r j L + â f j exp H-äG × Hr j + rbasis LL
= SG fcc ´ H1 + exp H-äG × rbasis LL
j j

= SG fcc ´ SG basis
Reflections are forbidden when SG total = 0 and are allowed otherwise. Let
G = Hv1 b1 + v2 b2 + v3 b3L and r j = Hx j a1 + y j a2 + z j a3L, so G × r j = 2 ΠHv1 x j + v2 y j + v3 z jL.
The atoms in the fcc lattice are located at {0,0,0}, {0,1/2,1/2}, {1/2,0,1/2}, and {1/2,1/2,0}
referenced to the cubic cell. Therefore,
SG fcc = f H1 + expH-äΠHv2 + v3LL + expH-äΠHv1 + v3LL + expH-äΠHv1 + v2LLL
From the above expression, we can see that if 8v1, v2, v3< are all even SG fcc = 4 f , if they are all
odd SG fcc = -2 f , and if they are mixed, SG fcc = 0. Meanwhile,

SG basis = f K1 + exp K-ä Hv1 + v2 + v3LOO

Π
2
which is zero when v1 + v2 + v3 = 2 n where n is an odd integer. Therefore, reflections are
allowed when 8v1, v2, v3< are all odd or all even such that v1 + v2 + v3 = 4 n where n is an
integer, otherwise SG total = 0.

Problem 4 (1 point)
Kittel Chapt. 2-6: Hydrogen atoms have a number density of nHrL = IΠa03M expH-2 r  a0L in
-1

the ground state where a0 is the Bohr radius. Show that the form factor is

fG = 16 ’ I4 + G2 a02M .
2
Kittel Chapt. 2-6: Hydrogen atoms have a number density of nHrL = IΠa03M expH-2 r  a0L in
-1

the ground state where a0 is the Bohr radius. Show that the form factor homework1.nb
is 3

fG = 16 ’ I4 + G2 a02M .
2

Ÿ Solution

From Eq. (42) in Kittel Chapt. 2, the form factor fG is fG = Ù dV nHrL expH-ä G × rL, which we
can rewrite as

fG = à à à dr dΘ dΦ r sinHΘL nHrL expH-ä G r cosHΘLL

¥ Π Π
2

expH-ä G rL - expH-ä G L
0 0 -Π

à
4Π ¥ -2 r
= dr exp r2
Π a0 3 0 a0 Gr
expH-ä G rL - expH-ä G L
à
4Π ¥ -2 r
= dr exp r2
Π a0 3 0 a0 Gr

à
4 ¥ -2 r
= dr exp r sinHG rL
G a0 3 0 a0

The integral can be evaluated in Mathematica as follows

4  HG * a0 ^ 3L * Integrate@r * Exp@- 2 * r  a0 D * Sin@G * rD,
8r, 0, ¥<, Assumptions ® 8a0 > 0 && G Î Reals<D
16

I4 + G2 a20 M
2

Problem 5 (2 points)
Kittel Chapt. 3-6: Using the appropriate constants in the text, calculate the cohesive energy of
KCl in the cubic ZnS structure described in Chapt. 1. Compare the value with that calculated for
KCl in the/ NaCl structure.

Ÿ Solution

First we need to obtain the equilibrium separation R0 for KCl in the ZnS structure. Then we can
evaluate the cohesive energy and compare it with the cohesive energy for KCl in its natural
form, which is the NaCl structure. From Table 7 in Chapt. 3 of Kittel we obtain
z Λ = 2.05 ´ 10-8erg for KCl in its natural state and the repulsive range parameter is Ρ = 0.326 Þ.
In the NaCl structure, each ion has z = 6 nearest neighbors, but in the ZnS structure each ion
only has 4 nearest neighbors. So, Hz ΛLZnS = 4  6 Hz ΛLNaCl = 1.37 ´ 10-8 erg, and from page 65
the Madelung constant for ZnS is Α = 1.6381. Using Eq. (23) in Kittel Chapt. 3 we can evaluate
the equlibrium distance for the KCl ions in the ZnS in cgs units as follows
z Λ = 2.05 ´ 10-8erg for KCl in its natural state and the repulsive range parameter is Ρ = 0.326 Þ.
the NaCl structure, each ion has z = 6 nearest neighbors, but in the ZnS structure each ion
In homework1.nb
only has 4 nearest neighbors. So, Hz ΛLZnS = 4  6 Hz ΛLNaCl = 1.37 ´ 10-8 erg, and from page 65
4

the Madelung constant for ZnS is Α = 1.6381. Using Eq. (23) in Kittel Chapt. 3 we can evaluate
the equlibrium distance for the KCl ions in the ZnS in cgs units as follows
zΛ = 1.3667 * 10 ^ - 8;
Ρ = 0.326 * 10 ^ - 8;
q = 4.8032 * 10 ^ - 10;
Α = 1.6381;

Solve@R0 ^ 2 * Exp@- R0  ΡD Š HΡ Α q ^ 2L  zΛ, R0 D

99R0 ® - 2.873 ´ 10-10 =, 9R0 ® 3.1511 ´ 10-10 =, 9R0 ® 3.00261 ´ 10-8 ==

Of the solutions presented only R0 = 3.00 Þ is a physical solution. The other positive one is too
small. Now we can use the R0 that we calculated for the ZnS structure to find the cohesive
energy per mole using Eq. (24) of Chapt. 3 of Kittel.
R0 = 3.00261 * 10 ^ - 8;
Na = 6.023 * 10 ^ 23;

- Na Α q ^ 2  R0 H1 - Ρ  R0 L

- 6.75775 ´ 1012

So the cohesive energy of KCl in the ZnS structure is

Utot ZnS = -6.44 ´ 1012 erg  mol = -161.5 kcal  mol = which is slightly less negative than the
calculated and experimental values of R0 for natural KCl shown in Table 7 of Chapt. 3,
Utot KCl calc = 161.6 kcal  mol and Utot KCl calc = 165.8 kcal  mol. Therefore, KCl’s natural struc-
ture is more energetically favorable than the ZnS structure, which explains why it does
not crystallize in the ZnS structure.

Problem 6 (1 point)
Kittel Chapt. 3-9: Show that the velocity of longitudinal waves in the [111] direction of a cubic
crystal is given by vx = @1  3 HC11 + 2 C12 + 4 C44L  ΡD12.

Ÿ Solution

The equation of motion for longitudinal waves in a cubic crystal is given by Eq. (57a) of Chapt.
3

+ HC12 + C44L
¶2 u ¶2 u ¶2 u ¶2 u ¶2 u ¶2 u
Ρ = C11 + C12 + +
¶t2 ¶ x2 ¶ y2 ¶ z2 ¶x ¶ y ¶x ¶z

A wave propagating in the [111] direction can be written as u = expJ-ä k

Hx + y + zLN.
3
Plugging u into the wave equation gives
 homework1.nb 5

- Ρ Ω2 = -C11 k 2 ‘ 3 + C12Ik 2 ‘ 3 + k 2 ‘ 3M + C44Ik 2 ‘ 3 + k 2 ‘ 3M

HC11 + 4 C12 + 2 C44L

2
k2
Ω =
3Ρ
So the wave velocity vx = Ω  k = @1  3 HC11 + 2 C12 + 4 C44L  ΡD12 as desired.

Problem 7 (2 points)
Kittel Chapt. 4-1: Consider a longitudinal wave us = u cosHΩ t - s K aL. a) Show that the total
energy of the wave is E = 1  2 M Ús Hdus  dtL2 + 1  2 C Ús Hus - us+1L2, where s runs over all
atoms. b) Use the dispersion relation to show that the time-averaged total energy per atom is
1  4 M Ω2 u2 + 1  2 CH1 - cosHK aLL u2 = 1  2 M Ω2 u2.

Ÿ Solution

a) The total energy is the sum of the kinetic and potential energies. The kinetic energy of atom s
is given by K.E. = 1  2 M Hdus  dtL2. Assuming the displacement between atoms is small the
potential energy of atom s can be written as P.E. = 1  2 CHus - us+1L2 + 1  2 CHus-1 - us L2,
where C is the spring constant between atoms. Summing the energies of all atoms and beging
careful not to double count potential energy terms we obtain
E = 1  2 M Ús Hdus  dtL2 + 1  2 C Ús Hus - us+1L2 as desired.
b) The time-average of cosHΘL2 is 1  2. So the time average of the kinetic energy for one atom is
K.E.atom = 1  4 M Ω2 u2. The potential energy contribution can be obtained by recognizing that
cosHΩ t - Hs + 1L K aL = cosHHΩ t - s K aL + K aL = cosHA + BL = cosHAL cosHBL - sinHAL sinHBL
where A = HΩ t - s K aL and B = K a. Then Hus - us+1L2 can be expanded as
TrigExpand@HCos@AD - Cos@A + BDL ^ 2D

Cos@AD2 1
1+ - Cos@BD - Cos@AD2 Cos@BD + Cos@AD2 Cos@BD2 -
2 2
Sin@AD2 1
+ Cos@BD Sin@AD2 - Cos@BD2 Sin@AD2 + 2 Cos@AD Sin@AD Sin@BD -
2 2
1 1
2 Cos@AD Cos@BD Sin@AD Sin@BD - Cos@AD2 Sin@BD2 + Sin@AD2 Sin@BD2
2 2

The time-average of cosHAL2 and sinHAL2 is 1  2, and the time average of cosHAL sinHAL is 0.
Therefore, the potential energy per atom is
P.E.atom = 1  2 C Ω2 u2 H1 - cosHK aLL
6 homework1.nb

P.E.atom = 1  2 C Ω2 u2 H1 - cosHK aLL

= 1  4 M Ω2 u2
So the time-average energy per atom is Eatom = K.E.atom+ P.E.atom = 1  2 M Ω2 u2 as desired.

Problem 8 (1 point)
Kittel Chapt. 4-2: Show that for long wavelengths the equation of motion (2) reduces to the
¶2 u ¶2 u
continuum elastic wave equation = v2 .
¶ t2 ¶ x2

Ÿ Solution

Eq. (2) from Kittel Chapt. 4 gives the equation of motion for an atom in plane s as

= CHus+1 + us-1 + us L
â 2 us
M
â t2
For long wavelengths we can approximate the atoms as a continuous medium and Taylor
âuHxL 1 â 2 uHxL
expand about x so us ® uHxL, us+1 ® uHx + â xL = uHxL + âx
âx + 2 âx2
â x2,
1 â 2 uHxL
â x2, M ® Ρ â x, and C ® K  â x, where Ρ is the
âuHxL
us-1 ® uHx - â xL = uHxL - âx
âx + 2 âx2
density and K is the bulk modulus. So changing to partial differentials

= HK  ΡL2
¶2 u ¶2 u
¶ t2 ¶ x2
2
¶2 u
=v
¶ x2

Problem 9 (2 point)
Kittel Chapt. 5-2: a) Estimate the root mean square thermal dialation for a primitive cell of
sodium. b) Use this result to estimate the root mean square thermal fluctuation of the lattice
parameter.

Ÿ Solution
1
The potential energy change per unit volume when a solid is compressed is U = 2
B ∆2, where
1 ∆a
3
∆= a
is the dialation along the cubic axes with a being the lattice constant of the bcc Na
crystal and B is the bulk modulus. (See Eq. (53) Chapt. 3). Since room temperature is well
above the Debye temperature, we can use the equipartition theorem. It states that any degree of
freedom that appears quadratically in the energy has an average energy of 1  2 kB T. Therefore,
kB T
V
= B ∆2 where ∆ is now the root mean square fluctuation of the dialation. Using
 1homework1.nb
The potential energy change per unit volume when a solid is compressed is U = 2
B ∆2, where7
1 ∆a
3
∆= a
is the dialation along the cubic axes with a being the lattice constant of the bcc Na
crystal and B is the bulk modulus. (See Eq. (53) Chapt. 3). Since room temperature is well
above the Debye temperature, we can use the equipartition theorem. It states that any degree of
freedom that appears quadratically in the energy has an average energy of 1  2 kB T. Therefore,
kB T
= B ∆2 where ∆ is now the root mean square fluctuation of the dialation. Using
kB = 1.38 ´ 10-16 erg  K, a = 4.23 Þ for Na and B = 7 ´ 1010 erg ‘ cm3 we calculate
V
∆a
a

Sqrt@1.38 * 10 ^ - 16 * 300  HH4.23 * 10 ^ - 8L ^ 3 * 7 * 10 ^ 10LD  3

0.0294659

∆a ∆V ∆a
Therefore, a
= 3 % and V
=3 a
= 9 %.