Problem statement:

The radial distribution function of a hard-sphere solid phase, which corresponds to the
probability of finding a second atom at a dimensionless distance r* from a central atom, is very
important in determining the thermodynamic properties of a solid phase.
For a hard-sphere solid with a face-centered cubic (FCC) structure, this radial distribution
function (as a function of r*), up to N shells, is given as follows:
N
ni
A1
2
1 *
g (r ) * exp
r r1
* * *
r
2
i 2 4 Ri r

exp r * Ri*
2

(1)

where * is the dimensionless number density, ni is the number of atoms in the i-th shell, and the
shell numbering is defined such that the equilibrium position of the i-th shell ( Ri* ) is given by

R
2
*
i

1
3

(2)

The number of atoms in i-th shell for an FCC crystal, up to the seventh shell, is known as
follows:
1
12

i
ni

2
6

3
24

4
12

5
24

6
8

7
48

In Eq. (1), is the Gaussian width parameter for peaks beyond the first shell, which can be
estimated from the density functional theory, and A1, 1, and r1 are the Gaussian parameters of
the first peak, which can be obtained by solving the following equations:

2 *

2
A1 exp 1 1 r1
3
2

(3)

A1
2

exp 1 r * r1 4r *2 dr * n1
*
r
2

(4)

Z hs 1

n1
2
1 *
*2
*
1 A1 exp 2 r r1 4r dr 0 4R1*

exp r * R1* 4r *2 dr *
2
2

(5)

where Zhs is the compressibility factor of the hard-sphere solid.

a. (50 points) Determine the Gaussian parameters of the first peak of an FCC hard-sphere crystal
for * = 1.079. At this density, the value of obtained from the density functional theory is
99.524 and the compressibility factor of the hard-sphere solid is known to be 12.445. After
obtaining the parameters of the first peak, plot the radial distribution function of the solid, i.e.
Eq. (1), up to seven shells (1 r* 2.5) along with the experimental Monte Carlo molecular
simulation data enlisted below:
r*
*

g(r )

1.0025

1.0125

1.0225

1.0325

1.0425

1.0625

1.0825

1.1025

1.1175

5.0516

5.0075

4.9287

4.8219

4.6978

4.3925

3.9818

3.5155

3.1279

r*

1.1275

1.1325

1.1375

1.1425

1.1475

1.1725

1.1825

1.1925

1.1975

g(r )

2.8766

2.7457

2.601

2.4825

2.3456

1.7466

1.5216

1.326

1.2202

r*

1.2325

1.3125

1.4125

1.5125

1.6125

1.8125

1.9125

2.0125

2.2125

0.6718

0.1351

0.2761

0.8005

0.621

1.6285

2.2111

0.9017

0.8305

g(r )

b. (50 points) If we want to obtain an accurate radial distribution function for this solid, instead
of using thermodynamic theories, i.e., density function theory and Eqs. (3), (4), and (5), we
could use a curve fitting method to fit the parameters A1, 1, r1, and in Eq. (1) to the Monte
Carlo simulation data directly. Find the values of these four parameters using a curve fitting
method. By using the obtained parameters, plot again the radial distribution function of the
solid up to seven shells (1 r* 2.5) along with the Monte Carlo simulation data.