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 
ξ ξ  
U (ξ) = 2N   0 0
X X
−  = 2N  α12 ξ 12 − α6 ξ 6 ,
j
pij j
pij

where ξ = σ/a; and α12 and α6 are corresponding Madelung constants:

(bcc) (fcc)
α6 = 12.2533 , α6 = 14.45392 ,
(bcc) (fcc)
α12 = 9.11418 , α12 = 12.13188 .
Minimizing the energy, we find:

∂U α62
= 0 ⇒ (ξ0 )6 = .
∂ξ 2α12

N  α62
U = − .
2 α12
(bcc)
!2 (fcc)
U (bcc) α6 α12
= = 0.95663 . . . .
U (fcc) α6
(fcc) (bcc)
α12

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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 − δ). Show that the
work done in compressing a unit length of the crystal has the leading term
Cδ 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 δ.)

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 δ 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) = λe−r/ρ ,
with λ = 0.3417 × 10−8 erg, ρ = 0.326 Å. If the structure is of the NaCl type,
then the Madelung constant is

NaCl structure: α = 1.747565 .

Calculate the cohesive energy of KCl in the ZnS structure (Chapter 1) in

which the Madelung constant is

ZnS structure: α = 1.6381

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and compare with the value calculated for KCl in the NaCl structure:
161.6 kcal/mol (Table 7).

Solution

We have
αq 2
U (ξ)/N = zλe−ξ − ,
ρξ
where ξ = R/ρ, z = 4. Minimizing,

∂U αq 2
= 0 ⇒ zλe−ξ0 = ,
∂ξ ρξ02

ξ0 − 1 αq 2
U (ξ0 ) = −N .
ξ02 ρ
To find the dimensionless number ξ0 , we need to solve

αq 2
ξ02 e−ξ0 = = 8.482 × 10−3 .
zλρ
We do it numerically by iterating

ξ0 = 4.770 + 2 ln ξ0 ,

till the process converges to ξ0 = 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 Kittel’s
book.