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 :
X 1 9.11418 X 1 12.2533
bcc: 12
= , = ,
j6=i
R a12 j6=i
R6 a6
X 1 12.13188 X 1 14.45392
fcc: 12
= , = .
j6=i
R a12 j6=i
R6 a6

Solution

!12 !6
 
U () = 2N  0 0
X X
= 2N  12 12 6 6 ,
j
pij j
pij

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

(bcc) (fcc)
6 = 12.2533 , 6 = 14.45392 ,
(bcc) (fcc)
12 = 9.11418 , 12 = 12.13188 .
Minimizing the energy, we find:

U 62
= 0 (0 )6 = .
212

N  62
U = .
2 12
(bcc)
!2 (fcc)
U (bcc) 6 12
= = 0.95663 . . . .
U (fcc) 6
(fcc) (bcc)
12

1
Hence, fcc is energetically preferable. Note, however, that the difference 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/Rn acting only between nearest neighbors. (a) Show
that at the equilibrium separation R0

2N q 2 (1 1/n) ln 2
U (R0 ) = . (1)
R0
(b) Let the crystal be compressed so that R0 R0 (1 ). Show that the
work done in compressing a unit length of the crystal has the leading term
C 2 /2, where

(n 1)q 2 ln 2
C = .
R02

Note: You should not expect to obtain this result from the expression for
U (R0 ), but must use the completer expression for U (R).

Solution

(a)

U (R) 2A 2q 2 X (1)m 2A 2q 2 ln 2
= n = n .
N R R m=1 m R R
P
Note that the fact that m=1 (1)m /m = ln 2 is readily seen from the
Taylor series

X (x)m
ln(1 + x) = .
m=1
m
Minimizing the energy, we find:
" #
U An q 2 ln 2
= 2N n+1 + .
R R R2

2
 U A q 2 ln 2
= 0 = ,
R R0n nR0
yielding the result (1).

(b) The work per unit length, W , is given by

U
W =
2N R0
where U is the energy difference and 2N R0 is the total length of the
system. At the point of minimum, the leading order for U is

1 2 U 
U (R)2 .
2 R2 R=R

0

(With our parameterization, R = R0 .)

We find " #
2U An(n + 1) 2q 2 ln 2
= 2N .
R2 Rn+2 R3

1 2 U  N
U = 3 (n 1)q 2 ln 2 .
2 R2 R=R

R0
0

Hence,
(n 1)q 2 ln 2 2
W = .
R02 2

3. Cubic ZnS structure

(problem 3.6 in Kittel)

For the short-range repulsion between K and Cl one has Ushort (r) = er/ ,
with = 0.3417 108 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
q 2
U ()/N = ze ,

where = R/, z = 4. Minimizing,

U q 2
= 0 ze0 = ,
02

0 1 q 2
U (0 ) = N .
02
To find the dimensionless number 0 , we need to solve

q 2
02 e0 = = 8.482 103 .
z
We do it numerically by iterating

0 = 4.770 + 2 ln 0 ,

till the process converges to 0 = 9.2105.

With N = NA 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.