Physics 715.

HW 3 Solutions
1. Cohesive energy of bcc and fcc neon
(problem 3.2 in Kittel)
Using the Lennard-Jones potential, calculate the ratio of the cohesive ener-
gies of neon in the bcc and fcc structures. The lattice sums are :
bcc:

j=i
1
R
12
=
9.11418
a
12
,

j=i
1
R
6
=
12.2533
a
6
,
fcc:

j=i
1
R
12
=
12.13188
a
12
,

j=i
1
R
6
=
14.45392
a
6
.
Solution
U() = 2N
_
_

_

p
ij
_
12

_

p
ij
_
6
_
_
= 2N
_

12

12

6
_
,
where = /a; and
12
and
6
are corresponding Madelung constants:

(bcc)
6
= 12.2533 ,
(fcc)
6
= 14.45392 ,

(bcc)
12
= 9.11418 ,
(fcc)
12
= 12.13188 .
Minimizing the energy, we nd:
U

= 0 (
0
)
6
=

2
6
2
12
.
U =
N
2

2
6

12
.
U
(bcc)
U
(fcc)
=
_

(bcc)
6

(fcc)
6
_
2

(fcc)
12

(bcc)
12
= 0.95663 . . . .
1
Hence, fcc is energetically preferable. Note, however, that the dierence is
only about 4%.
2. Linear ionic crystal
(problem 3.5 in Kittel)
Consider a long line of 2N ions of alternating charge q with a repulsive
potential energy A/R
n
acting only between nearest neighbors. (a) Show
that at the equilibrium separation R
0
U(R
0
) =
2Nq
2
(1 1/n) ln2
R
0
. (1)
(b) Let the crystal be compressed so that R
0
R
0
(1 ). Show that the
work done in compressing a unit length of the crystal has the leading term
C
2
/2, where
C =
(n 1)q
2
ln2
R
2
0
.
Note: You should not expect to obtain this result from the expression for
U(R
0
), but must use the completer expression for U(R).
Solution
(a)
U(R)
N
=
2A
R
n

2q
2
R

m=1
(1)
m
m
=
2A
R
n

2q
2
ln2
R
.
Note that the fact that

m=1
(1)
m
/m = ln2 is readily seen from the
Taylor series
ln(1 + x) =

m=1
(x)
m
m
.
Minimizing the energy, we nd:
U
R
= 2N
_

An
R
n+1
+
q
2
ln2
R
2
_
.
2
U
R
= 0
A
R
n
0
=
q
2
ln2
nR
0
,
yielding the result (1).
(b) The work per unit length, W, is given by
W =
U
2NR
0
where U is the energy dierence and 2NR
0
is the total length of the
system. At the point of minimum, the leading order for U is
U
1
2

2
U
R
2

R=R
0
(R)
2
.
(With our parameterization, R = R
0
.)
We nd

2
U
R
2
= 2N
_

An(n + 1)
R
n+2

2q
2
ln2
R
3
_
.
U
1
2

2
U
R
2

R=R
0
=
N
R
3
0
(n 1)q
2
ln2 .
Hence,
W =
(n 1)q
2
ln2
R
2
0

2
2
.
3. Cubic ZnS structure
(problem 3.6 in Kittel)
For the short-range repulsion between K and Cl one has U
short
(r) = e
r/
,
with = 0.341710
8
erg, = 0.326

A. If the structure is of the NaCl type,

then the Madelung constant is
NaCl structure: = 1.747565 .
Calculate the cohesive energy of KCl in the ZnS structure (Chapter 1) in
which the Madelung constant is
ZnS structure: = 1.6381
3
and compare with the value calculated for KCl in the NaCl structure:
161.6 kcal/mol (Table 7).
Solution
We have
U()/N = ze

q
2

,
where = R/, z = 4. Minimizing,
U

= 0 ze

0
=
q
2

2
0
,
U(
0
) = N

0
1

2
0
q
2

.
To nd the dimensionless number
0
, we need to solve

2
0
e

0
=
q
2
z
= 8.482 10
3
.
We do it numerically by iterating

0
= 4.770 + 2 ln
0
,
till the process converges to
0
= 9.2105.
With N = N
A
we then get U = 161.5 kcal/mol, which coincides (within
the accuracy of our calculation) with U = 161.6 kcal/mol of the Kittels
book.
4