PHY 491: Atomic, Molecular, and Condensed Matter Physics

Michigan State University, Fall Semester 2012

Solve by: Wednesday, November 14, 2012

Homework 9 – Solution

9.1. This problem on the cohesive energy of bcc and fcc neon compares the subtle difference between
different types of crystal structures for Lennard-Jones solids and is based on Kittel Chapter 3, Problem
#2. Using the Lennard-Jones potential, calculate the ratio of the cohesive energies of neon in the bcc
and fcc structures. The lattice sums are
X0 X0
C12 (bcc) = p−12
j = 9.11418 ; C6 (bcc) = p−6
j = 12.2533
j j

for the bcc lattice and

X0 X0
C12 (f cc) = p−12
j = 12.13188 ; C6 (f cc) = p−6
j = 14.45392
j j

for the fcc lattice.

Solution:

At the equilibrium interatomic separation,

!
C62
Ecoh = .
2C12

With the values for C12 and C6 provided, we get Ecoh (f cc) = ×8.6100 and Ecoh (bcc) = ×8.2368. Thus,

Ecoh (bcc) 8.2368

= = 0.957 .
Ecoh (f cc) 8.6100

9.2. This problem on solid molecular hydrogen is based on Kittel Chapter 3, Problem #3. For H2 one finds
from measurements on the gas that the Lennard-Jones parameters are  = 50×10−16 erg and σ = 2.96 Å.
Find the cohesive energy in kJ per mole of H2 ; do the calculation for an fcc structure. Treat each H2
molecule as a sphere. The observed value of the cohesive energy is 0.751 kJ/mol, much less than what
you get, so that quantum corrections must be very important.

Solution:

Ecoh 10−7 J
= 4×2.1525×NA = 4×50×10−16 erg× ×6.022×1023 ,
mol erg
Ecoh = 2.59 kJ/mol .

This value decreases significantly by quantum corrections, so it is reasonable to find the same melting
point for H2 and the much heavier rare gas Ne.

1
9.3. This problem involving the Madelung energy and repulsive energy for a linear ionic crystal is based
on Kittel Chapter 3, Problem #5. Consider a line of 2N ions of alternating charge ±q with a repulsive
potential energy A/Rn between nearest neighbors.

(a) Show that, in cgs units, at the equilibrium separation

2N q 2 ln 2 1
 
U (R0 ) = − 1− .
R0 n

(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 21 Cδ 2 , where, in cgs units,

(n − 1)q 2 ln 2
C= .
R0

To obtain the results in SI, replace q 2 by q 2 /4π0 . Note: Do not expect to obtain this result from the
expression for U (R0 ); you must use the complete expression for U (R).

Solution:

" #
ZA αq 2
U = N − with α = 2 ln 2 and Z = 2
Rn R
dU
= 0
dR
ZnA
R0n−1 =
αq 2
" #
N ZA
U (R0 ) = − αq 2
R0 R0n−1
2N ln 2 q 2 1
 
U (R0 ) = − 1− .
R0 n

Now we can expand U (R) near R = R0 . The linear terms vanish since the first derivative of U (R) vanishes
at R0 . The quadratic terms is the first correction.
" #
ZA αq 2
U (R) = U (R0 (1 + δ)) = N − ,
R0n (1 + δ)n R0 (1 + δ)
1 (n − 1)q 2 2 ln 2
U (R) = U (R0 (1 + δ)) = U (R0 ) + N δ 2 ,
2 R0
U (R) U (R0 ) 1 2 (n − 1)q 2 ln 2
= + Cδ with C = .
2N 2N 2 R0

9.4. This problem about ionic crystals and their most stable ionic configuration is based on Kittel Chapter
3, Problem #7. Barium oxide has the NaCl structure. Estimate the cohesive energies per molecule of
the hypothetical crystals Ba+ O− and Ba++ O−− with respect to separated neutral atoms. The observed
nearest-neighbor internuclear distance is R0 = 2.76 Å. The first and second ionization potentials of Ba
are 5.19 eV and 9.96 eV, respectively. The electron affinities of the first and second electrons added to
the neutral oxygen atom are 1.5 eV and −9.0 eV, respectively. The first electron affinity of the neutral

2
oxygen atom is the energy released in the reaction O+e →O− . The second electron affinity is the energy
released in the reaction O− + e →O−− . Which valence state do you predict will occur? Assume R0 is the
same for both forms, and neglect the repulsive energy.

Solution:

We have to first calculate the cohesive energy when the charges are ±1 e and ±2 e. Here we will calculate
the energy per dimer, U/N , because we will correct for the ionization energy and electron affinity for a
dimer.

We may ignore the short-range repulsion, which gives about a 10% correction, and focus on the main
Madelung energy. We will express the charge as |q| = e, where  = 1, 2. Then, for an fcc lattice,
!
U αq 2 1.747565 e2
=− =− 2 with  = 1, 2 .
N R0 2.76 1 Å

U
= −9.11 eV for  = 1 , (1)
N
U
= −36.44 eV for  = 2 . (2)
N
Clearly the +2/ − 2 charge state is more stable than the +1/ − 1 charge state due to the larger attraction
of the larger charges. But we should not forget the energies to produce a particular ionization state from
isolated neutral Ba and O atoms. Consequently, we need to combine the above results with the energy
investments associated with ionizing the isolated atoms.

For the charge state +1/ − 1 we get

Ba + 5.19 eV → Ba+ + e
O + e → O− + 1.5 eV
Ba + O → Ba+ + O− + (1.5 − 5.19) eV . (3)

Combining the results of Eq. (1) and Eq. (3) we get for the cohesive energy of a Ba+ O− fcc lattice

Ecoh (Ba+ O− ) = 9.11 eV − 3.69 eV = 5.42 eV .

Now consider the charge state +2/ − 2. We get

Ba + (5.19 + 9.96) eV → Ba++ + 2e

O + 2e → O−− + (1.5 − 9.0) eV
Ba + O → Ba++ + O−− − 22.65 eV . (4)

Combining the results of Eq. (2) and Eq. (4) we get for the cohesive energy of a Ba++ O−− fcc lattice

Ecoh (Ba++ O−− ) = 36.44 eV − 22.65 eV = 13.79 eV .

The cohesive energy of Ba++ O−− is obviously larger than that of Ba+ O− . So the more stable compound
is Ba++ O−− .