Homework #5

1. Quantum solid. In a quantum solid the dominant repulsive energy is the zero-point
energy of the atoms. Consider a crude of one-dimensional model of crystalline He4
with each He atom confined to a line segment of length L. In the ground state the
wave function within each segment is taken as a half wavelength of a free particle.
Find the zero point kinetic energy per particle.

Solution:
p 2 h 2 k 2 h 2 ( 2π ) 2 h2
ε= = = = .
2m 2m 2mλ2 2mλ2
λ h2 h2
With the assumption, L = . Then ε = = .
2 2m( 2 L) 2 8mL2

2. Cohesive energy of bcc and fcc neon. Using the Lennard-Jones potential, calculate
the ratio of the cohesive energies of neon in the bcc and fcc structures (Answer:
0.956). The lattice sums for the bcc structures are:

∑ 'p
j
−12
ij = 9.11418; ∑ 'p
j
−6
ij = 12.2533 .

Solution:
⎡ 1 ⎛σ ⎞
12
1 ⎛σ ⎞ ⎤
6
⎡ ⎛ σ ⎞12 ⎛σ ⎞ ⎤
6

U tot = 2 Nε ⎢∑ ' 12 ⋅ ⎜ ⎟ − ∑ ' 6 ⋅ ⎜ ⎟ ⎥ = 2 Nε ⎢α ⎜ ⎟ − β ⎜ ⎟ ⎥ .

⎣⎢ j pij ⎝ R ⎠ j pij ⎝ R ⎠ ⎦⎥ ⎣⎢ ⎝ R ⎠ ⎝ R ⎠ ⎦⎥
1 1
Here α ≡ ∑ ' 12 and β ≡ ∑ ' 6 .
j pij j pij
dU tot σ 12 σ6
Let = 0 . − 12α 13 + 6 β 7 = 0 This gives the equilibrium position R0 .
dR R R
σ6 β
= .
R6
0 2α
Substitute this into U tot , we have
⎡ ⎛ σ ⎞12 ⎛σ ⎞ ⎤
6
⎡ ⎛ β ⎞12 β ⎤ Nεβ 2
U tot = 2 Nε ⎢α ⎜ ⎟ − β ⎜ ⎟ ⎥ = 2 Nε ⎢α ⎜ ⎟ −β ⎥=− .
⎣⎢ ⎝ R ⎠ ⎝ R ⎠ ⎦⎥ ⎣⎢ ⎝ 2α ⎠ 2α ⎥⎦ 2α
Nεβ 2
The cohesive energy is − U tot = .
2α
− U tot (bcc ) 12.25332 / 9.11418 16.474
= = = 0.957 .
− U tot ( fcc ) 14.45392 / 12.13188 17.220
2
3. Solid molecular hydrogen. For H2 one finds from measurements on the gas that the
Lennard-Jones parameters are ε = 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 we calculated, so that quantum corrections must be very important.

Solution:
Nεβ 2 14.45392 2
U tot ( R0 ) = − = − Nε = −8.61Nε .
2α 2 × 12.13188
For 1 mol, N = 6.022 × 1023 ,
U tot ( R0 ) = −8.61 × 6.022 × 10 23 × 50 × 10 −16 = −2.59 × 1010 erg / mol = −2.59kJ / mol .

4. Liner ionic crystal. Consider a line of 2N ions of alternating charge ± q with a

repulsive potential energy A / R n between nearest neighbors. (a) Show that at the
equilibrium separation
2 Nq 2 ln 2 ⎛ 1 ⎞
(CGS) U ( R0 ) = − ⎜1 − ⎟ .
R0 ⎝ n⎠
(b) Let the crystal be compressed so that R0 → R0 (1 − δ ) . Show that the work done
in a compressing a unit length of the crystal has the leading term Cδ 2 / 2 , where
( n − 1) q 2 ln 2
(CGS) C= .
R0
To obtain the results in SI, replace q 2 by q 2 / 4πε 0 . Note: We should not expect to
obtain this result from the expression for U ( R0 ) , but we must use the complete
expression for U (R ) .

Solution:
(a)

-q +q -q +q -q +q

R
⎧ A q2
⎪⎪ n − r r / R = odd
u( R ) = ⎨ r 2
⎪A+q r / R = even
⎪⎩ r n r
1 ⎡ A ( −1) ij q 2 ⎤
p

U tot ( R ) = (2 N ) ⎢∑ ' n n + ∑ ' ⎥.

2 ⎢⎣ j pij R j pij R ⎥⎦
dU tot ( R ) ⎡ nA ( −1) ij q 2 ⎤
p

= − N ⎢∑ ' n n +1 + ∑ ' ⎥
dR ⎢⎣ j pij R j pij R 2 ⎥⎦

d 2U tot ( R ) ⎡ n( n + 1) A 2( −1) ij q 2 ⎤
p

= N ⎢∑ ' + ∑j p R 3 ⎥ .
'
dR 2 ⎢⎣ j pijn R n +2 ij ⎥⎦

dU tot ( R0 )
At equilibrium, = 0.
dR

( −1)
p ij

nA ( −1) q
pij 2
A
∑ '
pij q2
∑' + ∑' = 0, n = − ⋅
j
n n +1 2
.
1
j pij R0 j pij R0 R0
∑j ' p n nR0
ij

⎡ ( −1)
pij
⎤
⎢ ∑j ' p 2
( −1)
pij 2 ⎥
U tot ( R0 ) = N ⎢ − ∑ ' n
1 q q ⎥
⋅ + ∑' ⋅
ij
⎢ j pij 1 R0 ⎥
Then ⎢ ∑j ' p n nR0 j pij
⎥
⎣⎢ ij
⎦⎥
( −1)
pij
Nq 2 ⎛ 1⎞ 2 Nq 2 ⎛ 1 ⎞⎛ 1 1 1 1 ⎞
= ⎜1 − ⎟∑ ' = ⎜1 − ⎟⎜ − + − + − ... ⎟
R0 ⎝ n⎠ j pij R0 ⎝ n ⎠⎝ 1 2 3 4 ⎠

The factor 2 comes from negative j summation.

x2 x3 x4
Note ln(1 + x ) = x − + − + ... .
2 3 4

1 1 1
Let x=1, ln 2 = 1 − + − + ...
2 3 4

2 Nq 2 ln 2 ⎛ 1 ⎞
Therefore, U tot ( R0 ) = − ⎜1 − ⎟ .
R0 ⎝ n⎠

(b)

dU tot ( R0 ) 1 d 2U tot ( R0 )
U tot ( R ) = U tot ( R0 ) + ( R − R0 ) + ( R − R0 ) 2 + ...
dR 2 dR 2
1 d 2U tot ( R0 )
≈ U tot ( R0 ) + 2
( R − R0 ) 2
2 dR

Thus the work done by compress R0 → R0 (1 − δ ) equals the energy increase

 1 d 2U tot ( R0 ) 2 2
W = U tot ( R(1 − δ )) − U tot ( R0 ) ≈ R0 δ .
2 dR 2

From (a),

d 2U tot ( R0 ) ⎡ n ( n + 1) A 2( −1) ij q 2 ⎤
p
= N ⎢∑ ' n n+2
+ ∑j p R 3 ⎥⎥
'
dR 2 ⎢⎣ j pij R0 ij 0 ⎦
⎡ ( −1)
pij
⎤
⎢ ∑' pij ( n + 1) q 2
⎥
2( −1) q 2 ⎥
pij
= N ⎢− ∑ ' n
1
⋅ + ∑'
j

⎢ j pij 1 nR03 pij R03 ⎥

⎢ ∑j ' p n j
⎥
⎢⎣ ij ⎥⎦
( −1)
pij
Nq 2 2 Nq 2
= 3
[2 − ( n + 1)]∑ ' = ( n − 1) ln 2
nR0 j pij nR03

1 d 2U tot ( R0 ) 2 2 Nq 2
Then W = 2
R0 δ = ( n − 1) ln 2 ⋅ δ 2 . There are 2N atoms. The work
2 dR nR0
done to each atom is

W q2 1 q2
w= = ( n − 1) ln 2 ⋅ δ 2 = Cδ 2 with C = ( n − 1) ln 2 .
2 N 2nR0 2 nR0