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.
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
angle between two vectors satisfies cos() =
v
1
v
2
v
1
v
2

.
v1 = 1, 1, 1;
v2 = 1, -1, -1;
ArcCosv1.v2 Normv1 + Normv2 + 180 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?
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 x, y, z basis. Following the rules in Kittel, we note that the vectors a
1
and a
3
intersect the (100) plane and their lengths will have a 1:1 ratio at the points of intersection.
Therefore, (100) in the x, y, z basis becomes (101) in the a
1
, a
2
, a
3
basis. Similarly,
vectors a
2
and a
3
intersect the (001) plane and their lengths also have a 1:1 ratio at the points of
intersection. So, (001) in the x, y, z basis becomes (011) in the a
1
, a
2
, a
3
basis.
Problem 3 (2 points)
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 v
1
+ v
2
+ v
3
= 4 n where all indices are even and n is an integer, otherwise all
indices are odd.
Solution
The structure factor is defined as S
G
= _
j
f
j
exp(i G r
j
), 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
S
Gtotal
= S
Gfcc 1
+ S
Gfcc 2
= _
j
f
j
exp (iG r
j
) + _
j
f
j
exp (iG (r
j
+ r
basis
))
= S
Gfcc
(1 + exp (iG r
basis
))
= S
Gfcc
S
Gbasis
Reflections are forbidden when S
Gtotal
= 0 and are allowed otherwise. Let
G = (v
1
b
1
+ v
2
b
2
+ v
3
b
3
) and r
j
= (x
j
a
1
+ y
j
a
2
+ z
j
a
3
), so G r
j
= 2 (v
1
x
j
+ v
2
y
j
+ v
3
z
j
).
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,
S
Gfcc
= f (1 + exp(i(v
2
+ v
3
)) + exp(i(v
1
+ v
3
)) + exp(i(v
1
+ v
2
)))
From the above expression, we can see that if v
1
, v
2
, v
3
are all even S
Gfcc
= 4 f , if they are all
odd S
Gfcc
= 2 f , and if they are mixed, S
Gfcc
= 0. Meanwhile,
S
Gbasis
= f _1 + exp _i

2
(v
1
+ v
2
+ v
3
)
which is zero when v
1
+ v
2
+ v
3
= 2 n where n is an odd integer. Therefore, reflections are
allowed when v
1
, v
2
, v
3
are all odd or all even such that v
1
v
2
v
3
4 n where n is an
integer, otherwise S
Gtotal
0.
Problem 4 (1 point)
Kittel Chapt. 2-6: Hydrogen atoms have a number density of n(r) = |a
0
3
]
1
exp(2 r f a
0
) in
the ground state where a
0
is the Bohr radius. Show that the form factor is
f
G
= 16 |4 + G
2
a
0
2
]
2
.
2 homework1.nb
Kittel Chapt. 2-6: Hydrogen atoms have a number density of n(r) = |a
0
3
]
1
exp(2 r f a
0
) in
the ground state where a
0
is the Bohr radius. Show that the form factor is
f
G
= 16 |4 + G
2
a
0
2
]
2
.
Solution
From Eq. (42) in Kittel Chapt. 2, the form factor f
G
is f
G
=
]
dVn(r) exp(i G r), which we
can rewrite as
f
G
=
_
0
o
_
0

dr d d r
2
sin() n(r) exp(i G r cos())
=
4
a
0
3
_
0
o
dr exp
2 r
a
0
r
2
exp(i G r) exp(i G )
G r
=
4
a
0
3
_
0
o
dr exp
2 r
a
0
r
2
exp(i G r) exp(i G )
G r
=
4
G a
0
3
_
0
o
dr exp
2 r
a
0
r sin(G r)
The integral can be evaluated in Mathematica as follows
4 G + a
0
^3 + Integrater + Exp-2 + r a
0
+ SinG + r,
r, 0, , Assumptions - a
0
> 0 && G e Reals
16
4 G
2
a
0
2

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.
Solution
First we need to obtain the equilibrium separation R
0
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 = 2.05 10
8
erg for KCl in its natural state and the repulsive range parameter is = 0.326 .
In the NaCl structure, each ion has z = 6 nearest neighbors, but in the ZnS structure each ion
only has 4 nearest neighbors. So, (z )
ZnS
= 4 f 6 (z )
NaCl
= 1.37 10
8
erg, and from page 65
the Madelung constant for ZnS is = 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
homework1.nb 3
First we need to obtain the equilibrium separation R
0
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 = 2.05 10
8
erg for KCl in its natural state and the repulsive range parameter is = 0.326 .
In the NaCl structure, each ion has z = 6 nearest neighbors, but in the ZnS structure each ion
only has 4 nearest neighbors. So, (z )
ZnS
= 4 f 6 (z )
NaCl
= 1.37 10
8
erg, and from page 65
the Madelung constant for ZnS is = 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 = 1.3667 + 10^-8;
= 0.326 + 10^-8;
q = 4.8032 + 10^-10;
= 1.6381;
SolveR
0
^2 + Exp-R
0
= q^2 z, R
0

R
0
2.873 10
10
, R
0
3.1511 10
10
, R
0
3.00261 10
8

Of the solutions presented only R

0
= 3.00 is a physical solution. The other positive one is too
small. Now we can use the R
0
that we calculated for the ZnS structure to find the cohesive
energy per mole using Eq. (24) of Chapt. 3 of Kittel.
R
0
= 3.00261 + 10^-8;
Na = 6.023 + 10^23;
-Na q^2 R
0
1 - R
0

6.75775 10
12
So the cohesive energy of KCl in the ZnS structure is
U
tot ZnS
= 6.44 10
12
erg f mol = 161.5 kcal f mol = which is slightly less negative than the
calculated and experimental values of R
0
for natural KCl shown in Table 7 of Chapt. 3,
U
tot KCl calc
= 161.6 kcal f mol and U
tot KCl calc
= 165.8 kcal f mol. Therefore, KCls 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 v
x
= [1 f 3 (C
11
+ 2 C
12
+ 4 C
44
) f ]
1f2
.
Solution
The equation of motion for longitudinal waves in a cubic crystal is given by Eq. (57a) of Chapt.
3

o
2
u
ot
2
= C
11
o
2
u
ox
2
+ C
12
o
2
u
o y
2
+
o
2
u
oz
2
+ (C
12
+ C
44
)
o
2
u
ox o y
+
o
2
u
ox oz
A wave propagating in the [111] direction can be written as u = expi
k
3
(x + y + z).
Plugging u into the wave equation gives
4 homework1.nb

2
= C
11
k
2
3 + C
12
|k
2
3 + k
2
3] + C
44
|k
2
3 + k
2
3]

2
=
k
2
3
(C
11
+ 4 C
12
+ 2 C
44
)
So the wave velocity v
x
= f k = [1 f 3 (C
11
+ 2 C
12
+ 4 C
44
) f ]
1f2
as desired.
Problem 7 (2 points)
Kittel Chapt. 4-1: Consider a longitudinal wave u
s
= u cos(t s K a). a) Show that the total
energy of the wave is E = 1 f 2 M _
s
(du
s
f dt)
2
+ 1 f 2 C _
s
(u
s
u
s+1
)
2
, where s runs over all
atoms. b) Use the dispersion relation to show that the time-averaged total energy per atom is
1 f 4 M
2
u
2
+ 1 f 2 C(1 cos(K a)) u
2
= 1 f 2 M
2
u
2
.
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 f 2 M (du
s
f dt)
2
. Assuming the displacement between atoms is small the
potential energy of atom s can be written as P.E. = 1 f 2 C(u
s
u
s+1
)
2
+ 1 f 2 C(u
s1
u
s
)
2
,
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 f 2 M _
s
(du
s
f dt)
2
+ 1 f 2 C _
s
(u
s
u
s+1
)
2
as desired.
b) The time-average of cos()
2
is 1 f 2. So the time average of the kinetic energy for one atom is
K.E.
atom
= 1 f 4 M
2
u
2
. The potential energy contribution can be obtained by recognizing that
cos(t (s + 1) K a) = cos((t s K a) + K a) = cos(A + B) = cos(A) cos(B) sin(A) sin(B)
where A = (t s K a) and B = K a. Then (u
s
u
s+1
)
2
can be expanded as
TrigExpandCosA - CosA + B^2
1
CosA
2
2
CosB CosA
2
CosB
1
2
CosA
2
CosB
2

SinA
2
2
CosB SinA
2

1
2
CosB
2
SinA
2
2 CosA SinA SinB
2 CosA CosB SinA SinB
1
2
CosA
2
SinB
2

1
2
SinA
2
SinB
2
The time-average of cos(A)
2
and sin(A)
2
is 1 f 2, and the time average of cos(A) sin(A) is 0.
Therefore, the potential energy per atom is
P.E.
atom
= 1 f 2 C
2
u
2
(1 cos(K a))
homework1.nb 5
P.E.
atom
= 1 f 2 C
2
u
2
(1 cos(K a))
= 1 f 4 M
2
u
2
So the time-average energy per atom is E
atom
= K.E.
atom
+P.E.
atom
= 1 f 2 M
2
u
2
as desired.
Problem 8 (1 point)
Kittel Chapt. 4-2: Show that for long wavelengths the equation of motion (2) reduces to the
continuum elastic wave equation
o
2
u
o t
2
= v
2
o
2
u
o x
2
.
Solution
Eq. (2) from Kittel Chapt. 4 gives the equation of motion for an atom in plane s as
M
d
2
u
s
dt
2
= C(u
s+1
+ u
s1
+ u
s
)
For long wavelengths we can approximate the atoms as a continuous medium and Taylor
expand about x so u
s
u(x), u
s+1
u(x + dx) = u(x) +
du(x)
dx
dx +
1
2
d
2
u(x)
dx
2
dx
2
,
u
s1
u(x dx) = u(x)
du(x)
dx
dx +
1
2
d
2
u(x)
dx
2
dx
2
, M dx, and C K f dx, where is the
density and K is the bulk modulus. So changing to partial differentials
o
2
u
o t
2
= (K f )
2
o
2
u
o x
2
= v
2
o
2
u
o x
2
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.
Solution
The potential energy change per unit volume when a solid is compressed is U =
1
2
B
2
, where
1
3
=
a
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 f 2 k
B
T. Therefore,
k
B
T
V
= B
2
where is now the root mean square fluctuation of the dialation. Using
k
B
= 1.38 10
16
erg f K, a = 4.23 for Na and B = 7 10
10
erg cm
3
we calculate
a
a
6 homework1.nb
The potential energy change per unit volume when a solid is compressed is U =
1
2
B
2
, where
1
3
=
a
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 f 2 k
B
T. Therefore,
k
B
T
V
= B
2
where is now the root mean square fluctuation of the dialation. Using
k
B
= 1.38 10
16
erg f K, a = 4.23 for Na and B = 7 10
10
erg cm
3
we calculate
a
a
Sqrt1.38 + 10^-16 + 300 4.23 + 10^-8^3 + 7 + 10^10 3
0.0294659
Therefore,
a
a
= 3 % and
V
V
= 3
a
a
= 9 %.
homework1.nb 7