Radial Distribution Function for Argon: Calculations from Thermodynamic

Properties and the LennardJones 6:12 Potential

Bruce W. Davis

Citation: The Journal of Chemical Physics 54, 4616 (1971); doi: 10.1063/1.1674731
View online: http://dx.doi.org/10.1063/1.1674731
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 4616 E. E. GENSEl<.

present to attenuate the effect of the surrounding
charges on these nuclei.
* Present address: Department of Chemistry, California State
College, Hayward, Hayward, Calif. 94542.
1 W. H. Baur, Am. Mineralogist 49,697 (1964).
2 G. R. Eulcnberger, D. P. Shoemaker, and J. G. Keil, J. Phys.
Chern. 71,1812 (1967).
3J. H. Van Vleck, Phys. Rev. 74,61 (1948).
4A. Abragam, Principles of Nuclear M aguetism (Oxford,
England, Clarendon, 1961), p. 130.
5 T. P. Das and E. L. Hahn, Solid State Phys., Supp!. 1, 120
(1958) .
6 N. Bloembergen and T. J. Rowland, Acta Met. 1, 731 (1953).
7 N. B1ocmbergen, E. M. Purcell, and R. V. Pound, Phys. Rev.
73, 27 (1948).

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 54, NUMBER 11 1 JUNE 1971

Radial Distribution Function for Argon: Calculations from Thermodynamic Properties and
the Lennard-Jones 6 :12 Potential
BRUCE W. DAVIS*
School of Chemistry, Georgia Institute of Technology, Atlanta, Georgia 30332
(Received 14 January 1971)

The radial distribution function, g(x), of argon is calculated from thermodynamic data and the Lennard-
Jones 6: 12 potential. This is accomplished by introducing analytical expressions for the function Y(x) ""
exp[<t> (x)/T*Jg(x) -1 which contain a limited number of adjustable parameters. Three calculations are
made. The first uses only the pressure and energy equations and reproduces g(x) accurately for x~ 1.5.
The other two incorporate the compressibility equation and generally give accurate values of g(x) for
x~2.1 and approximate values for 2.1~x~3.

I. INTRODUCTION accuracy of the expression for Vex) over an adequate

1 range of x. Calculations in this work are based on
It is well known that the pressure, energy, and
truncated versions of two exact series expansions for
isothermal compressibility of a monatomic fluid may
V(x), one of which is due to Widom. 8 Three calcula-
be written in terms of integral equations involving the
tions are carried out. The first of these utilizes only the
radial distribution function, g(x), and the pair potential
energy and pressure equations in conjunction with the
or its derivative. The only assumptions implicit in
LJ potential. This procedure reproduces g(x) at rela-
these equations are that the total potential energy is
tively short range, i.e., x:S: 2. The second and third
given by the sum of N(N-l)j2 pair potentials and
calculations bring in the compressibility equation and
that quantum effects may be neglected. Although
attempt to calculate g(x) over a more extended range,
neither of these assumptions is seriously in error for
i.e., x:S:3.
argon, it should be recognized that it is probably not
possible to find a pair potential which is altogether
II. SHORT-RANGE SOLUTION OF g(x)
consistent with thermodynamic data. 2 Nonetheless it is
CONSISTENT WITH THE LJ POTENTIAL
common practice to calculate thermodynamic quan-
tities from some model potential, such as a Lennard- General expressions for the reduced thermodynamic
Jones 6: 12 (LJ) potential, and from values of g(x) variables Z* and U* may be derived from statistical
determined by ~ome incomplete formulation, such as mechanics l and are given by
the hypernetted chain (RNC) or Percus-Yevick (PY)
approximation. 3- 6 The latter method generates thermo-
1 27[n*
Z*= 1- - - -
/00 xcp'(x)g(x)x dx
2 (2.1)
dynamic quantities accurately for densities up to the 3 T* 0

critical density and a little beyond in most instances. and

Another approach 7 yields both thermodynamic prop-
erties and g(x) by performing computer "experiments" C* = 27[n* /'" cp(x) g(x) x2dx, (2.2)
on a system of particles having only pairwise inter- o
actions corresponding to the LJ or some other potential. where n*=lVro3/V, T*=kT/E, x=r/ro, cp(x) =U(X)/E,
In the present work a still different technique is Z*=PV/NkT, U*=U/NE, and p*=prNE are the
adopted, namely experimental thermodynamic data definitions of the reduced variables.
are used to calculate g(x) assuming that pairwise Expressions (2.1) and (2.2) may now be specialized
interaction is represented by the LJ potential. A good by introducing the LJ potential. This results in
approximation for g(x) can be achieved by introducing 167[n*
analytical expressions for the function Z*=I+ - -
T*
v (x) == exp[cp(x) /T*Jg(x) -1, (1.1)
which contain only a limited number of adjustable
parameters. The success of the method depends on the

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 R.\DI.\L DISTRIB1JTIOK FU:--JCTION FOR .\RGON 4617

TABLE 1. Values of the thermodynamic variables CI and C2 •

T*= 1.3 T*= 1.4 T*=1.5

n* CI " C," CIa C,' CIa C2"

0.050 0.5847 0.2513 0.5604 0.2421 0.5420 0.2356

0.100 0.5795 0.2512 0.5535 0.2412 0.5350 0.2346
0.150 0.5723 0.2503 0.5451 0.2395 0.5270 0.2331
0.200 0.5627 0.2482 0.5356 0.2373 0.5179 0.2310
0.250 0.5509 0.2450 0.5248 0.2345 0.5093 0.2292
0.300 0.5366 0.2405 0.5138 0.2315 0.5012 0.2275
0.325 0.5290 0.2379 0.5088 0.2302 0.4977 0.2271
0.350 0.5215 0.2353 0.5044 0.2291 0.4947 0.2268
0.400 0.5080 0.2309 0.4970 0.2279 0.4906 0.2273
0.450 0.4993 0.2290 0.4927 0.2284 0.4890 0.2294
0.500 0.4952 0.2297 0.4919 0.2311 0.4904 0.2334
0.550 0.4957 0.2332 0.4948 0.2362 0.4947 0.2396
0.575 0.4981 0.2364 0.4974 0.2397 0.4980 0.2437
0.600 0.5010 0.2401 0.5010 0.2440 0.5020 0.2483
0.625 0.5047 0.2445 0.5052 0.2488 0.5066 0.2535

a Based on Ref. 9.

and 'It is the potential energy of a test molecule with the

remaining molecules in a system as a function of the
U*=87rn* (_ ~oo g(x)x-4dx+ ~oo g(X)X-lOdX). (2.4) positions of all the molecules, and the kth derivative of
exp( -'It/kT) is a directional derivative in an arbi-
Solving (2.3) and (2.4) for the integrals in g(x) it is trarily chosen direction, q. Widom lO has also shown
seen that that ao:?: 1, therefore it is convenient to define the

1 o
00

g(x)x-4dx=C1 (2.5)
positive quantity aOl=ao-l. If (2.9) is truncated at
k= 2 it follows that

and (2.11)

Obviously a truncated form such as (2.11) will hold

where C1 and C2 are defined in terms of reduced thermo-
dynamic variables by
C1 = [T*(Z*-1) -4U*J/167rn*
and
C 2 = [T*(Z*-1) - 2U*J/167rn*.
The evaluation of C1 and C2 from experiment can be
accomplished in a straightforward fashion utilizing
the reduced argon data of Levelt. 9 C1 and C2 are sum-
marized for three temperatures in Table 1. Notice that
the integrals (2.5) and (2.6) are determined primarily
by the short-range behavior of g(x), since the inte-
grands quickly become small for x greater than l.
In order to apply (2.5) and (2.6) it is necessary to
represent V (x) [or less satisfactorily g( x) J as a suitable
function of x. Widom8 has shown that
00
(2.6)
only over a limited range of x. As a result it is necessary
to specify the range over which (2.11) can be expected
to reproduce Vex). The following approximation IS
proposed:
(2.7)
(2.8) 2<x, Vex) =0. (2.12)
It can be observed both from x-ray diffraction resultsl l
and from the HNC and PY results3- 6 that V(2) is
very nearly zero for a wide range of thermodynamic
states. For this reason an additional semiempirical
restriction is placed on (2.12), namely that there be no
discontinuity in Vex) at x=2. This latter boundary
condition along with (2.5) and (2.6) permit explicit
calculation of the three adjustable constants in (2.12).
It should be noted that (2.12) is to be used only to
evaluate the short-ranged integrals (2.5) and (2.6),

l+V(x)= L: (-1)kakx2k, (2.9) the exact choice of truncation not being extremely
k~O important. The choice made, however, seems quite
where reasonable and the subsequent calculations confirm it.
Calculations proceed by first writing (2.5) and
ak= (z/n) 2 (ro2k/2k !) (2.6) in the special form required by (2.12),
X <{ (Clk /Clqk) [exp( -'It /kT) J12). (2.10) (2.13)

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 4618 BRUCE W. DAVIS

TABLE II. Numerical values of integrals of the type, solving Eqs. (2.13), (2.16), and (2.20) simultaneously

f exp (;*4 (X-

12 6
_X- ) ) xmdx.
using the data in Tables I and II. These solutions are
summarized in Table III.
The values of g(x) may be calculated from the
constants listed in Table III. It is interesting to see how
In a T*= 1.3 T*= 1.4 T*= 1. 5 well these results agree with the PY -LJ calculations of
Throop and Bearman." Comparison between Ref. 6 and
-10 0.23532 0.23038 0.22671 g(x) obtained from the parameters of Table III is
-4 0.55644 0.54102 0.52848 made in Table IV for T*= 1.5. Comparable agreement
-10 2 0.23509 0.23016 0.22649 is found at other temperatures. Notice that the two
-8 2 0.28588 0.27856 0.27286 methods of calculating g(x) differ by a few percent at
-6 2 0.36824 0.35765 0.34919 most for x:::; 1.5, but may differ by as much as 20%
-4 2 0.51410 0.49873 0.48623 for 1.5 < x:::; 2.0. Inaccuracy in the present method is
-2 2 0.80253 0.77964 0.76081 due in part to the semiempirical boundary condition
0 2 1.44689 1. 41112 1.38144 at x = 2 and in part to the assumption that Y (x) = 0 for
-10 3 0.23531 0.23038 0.22671 x> 2. The latter assumption becomes progressively
-8 3 0.28696 0.27964 0.27394 worse with increasing density as second and higher
-6 3 0.37380 0.36321 0.35473 coordination shells exert pwgressively greater influence
-4 3 0.54408 0.52866 0.51612 in determining the shape of Y (x). Error is also in tro-
-2 3 0.97244 0.94932 0.93029 duced by the inability of (2.12) to adequately represent
0 3 2.46366 2.42667 2.39594 Y(x) over the entire range 0:::; x:::; 2. Comparison of
+2 3 9.4900 9.4233 9.3673 the present method with the PY results is complicated
+4 3 50.277 50.128 50.002 by the incomplete nature of the PY theory. Agreement
+6 3 318.27 317.82 317.43
between the two methods can be considered quite
+8 3 2213.5 2211.5 2209.8
16253. 16243. 16233.
satisfactory and in fact might be considered remarkable
+10 3
for x less than 1.5.
Experimental values of g(x) have been determined
where from x-ray diffraction by Mikolaj and PingsY Several
thermodynamic states included in their data are quite
II = JOC (-~(x)) 4
0 exp T* x- dx (2.14) close to some given here. For example, the experimental
g(x) 12 for T*= 1.28 and n*=0.32 is compared in Fig. 1
and with results from Eq. (2.12) for T*= 1.3 and n*=O.32S.
The agreement is quite good, calculations from (2.12)
I n+2 = [ 0 exp (-~(x))
T* X-
4 2n
x dx, n=O, 1, 2; (2.15) differing from the x-ray diffraction data by only a few
percent. In Fig. 2 a similar comparison is made between
(2.16) the x-ray diffraction results for T*= 1.28 and n*=O.S4
where and the results of (2.12) and those from the PY theory
at T*= 1.3 and n*=O.S5. The present method actually
(2.17) agrees somewhat more closely with the experimental
points than does the PY theory for x:::; 1.5. The com-
and

n=0,1,2. (2.18)
T* = 1.3
n* =0.325
The restriction that there be no discontinuity in
(2.12) yields still another equation, namely
2
I~ - Eq. (2.12)
• X·ray Diffraction
aOl-4al+ 16az=0. (2.19) i\
Equations (2.13), (2.16), and (2.20) provide a solution
for Y(x) since there are three equations in three un-
g(x)
'\.. .' ....... .
knowns.
It is then easy to calculate g(x) from (1.1) and
(2.12). The integrals of the type I and J above are
conveniently solved numerically by Simpson's rule
integration for the case of the LJ potential. The oo~--~~J~1~--L---~2----L-~3
integrals needed here as well as some needed in Sees. x
III and IV are given in Table II for three temperatures. FIG. 1. g(x) computed from Eq. (2.12). The x-ray diffraction
Explicit values for aOl, ai, and az are then obtained by points are from Mikolaj and Pings for T* = 1.28 and n* = 0.32.

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 RADIAL DISTRIBUTION FUNCTION FOR ARGON 4619

TABLE III. The constants am, a" and a2 for Eq. (2.12).

T*= 1.3 T*=1.4 T*=1.5

-----------
n* aOl a, a, aOl a, a2 aOl a, a2

0.050 0.1379 0.0683 0.0085 0.1210 0.0709 0.0102 0.1095 0.0728 0.0114
0.100 0.2227 0.1616 0.0265 0.2043 0.1673 0.0290 0.2295 0.2052 0.0370
0.150 0.3105 0.2624 0.0462 0.2824 0.2620 0.0479 0.2707 0.2641 0.0491
0.200 0.3935 0.3640 0.0664 0.3600 0.3589 0.0672 0.3461 0.3586 0.0680
0.250 0.4698 0.4641 0.0867 0.4367 0.4580 0.0872 0.4245 0.4548 0.0872
0.300 0.5384 0.5624 0.1069 0.5091 0.5534 0.1065 0.4981 0.5451 0.1052
0.325 0.5672 0.6073 0.1164 0.5444 0.5991 0.1157 0.5428 0.5965 0.1152
0.350 0.5942 0.6503 0.1254 0.5773 0.6410 0.1242 0.5827 0.6422 0.1241
0.400 0.6538 0.7382 0.1437 0.6575 0.7355 0.1428 0.6722 0.7382 0.1425
0.450 0.7284 0.8296 0.1619 0.7504 0.8349 0.1618 0.7803 0.8461 0.1628
0.500 0.8254 0.9322 0.1815 0.8684 0.9503 0.1833 0.9098 0.9674 0.1850
0.550 0.9527 1.0533 0.2038 1.0157 1.0852 0.2078 1.0741 1.1152 0.2117
0.575 0.9521 1. 0473 0.2023 1.1064 1.1663 0.2224 1.1749 1. 2043 0.2276
0.600 0.7592 0.8553 0.1664 1. 2109 1.2583 0.2389 1.2829 1.2986 0.2445
0.625 0.5255 0.6223 0.1227 1.3244 1. 3576 0.2566 1.4037 1.4038 0.2632

parison is not completely valid, since the diffraction
data correspond to a slightly different thermodynamic
state. It is clear from all the above comparisons that
calculations based on ( 2.12) provide an accurate
solution of g(x) for x~ 1.5.
III. A LONGER-RANGE SOLUTION OF g(x)
Besides the short-ranged integrals provided by (2.5)
and (2.6), it is also possible to write down an integral
dependent on the long-range behavior of g(x). This is

TABLE IV. g(x) from Eq. (2.12) and from the PY approximation for T*=1.5.

n*

0.10 0.25 0.40 0.55

x (2.12) pya (2.12) pya (2.12) pya (2.12) pya

0.90 0.013 0.013 0.013 0.014 0.014 0.016 0.016 0.020

0.95 0.291 0.283 0.294 0.301 0.304 0.332 0.336 0.398
1.00 1.061 1.028 1.057 1.068 1.077 1.140 1.171 1.316
1.05 1. 737 1.679 1.705 1.701 1.709 1. 764 1.826 1.957
1.10 1.994 1.927 1.930 1. 909 1. 903 1.924 1.993 2.051
1.15 1. 968 1.904 1.877 1.848 1.819 1.815 1.865 1.861
1. 20 1.830 1. 775 1. 721 1.692 1.639 1.624 1.643 1.607
1.25 1.673 1.628 1.552 1.529 1.452 1.438 1.421 1.380
1.30 1.531 1.496 1.402 1.389 1.289 1.284 1.230 1.202
1.35 1.413 1.388 1.279 1.276 1.156 1.165 1.076 1.070
1.40 1.318 1.301 1.180 1.188 1.051 1.076 0.954 0.977
1.45 1.242 1.234 1.103 1.122 0.969 1.011 0.859 0.913
1.50 1.182 1.181 1.043 1.073 0.907 0.966 0.788 0.873
1.55 1.135 1.140 0.998 1.037 0.862 0.935 0.737 0.850
1.60 1.099 1.109 0.966 1.012 0.832 0.917 0.704 0.841
1.65 1.071 1.086 0.944 0.996 0.815 0.908 0.688 0.843
1. 70 1.051 1.069 0.932 0.987 0.811 0.908 0.688 0.855
1. 75 1.037 1.057 0.929 0.984 0.819 0.915 0.704 0.875
1.80 1.028 1.048 0.935 0.986 0.838 0.927 0.737 0.901
1.85 1.024 1.044 0.949 0.992 0.870 0.945 0.786 0.932
1. 90 1.026 1.042 0.971 1.003 0.914 0.967 0.853 0.969
1. 95 1.032 1.043 1.002 1.016 0.971 0.992 0.938 1.007
2.00 1.042 1.045 1.042 1.031 1.042 1.017 1.042 1.004

a Reference 6.

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 4620 B Rue E \\". DAY I S

devices for fixing the adjustable parameter suggest

P=1.3
themselves. One is to set Y(2) =0 as was done in the
n* =0.55
2 previous section, another is to force Y(2) into agree-
- Eq. (3.5)
ment with the PY or HNC theory for each thermo-
o Eq.(2.12) dynamic state, and a third is to artificially adjust
o py
Y(x) so that the maximum in g(x) always occurs at
g(x) • X.raY!1iffraction x= 21/ 6 • Other reasonable but arbitrary ways of fixing
the adjustable parameter also come to mind, however
sample calculations indicate that setting Y(2) =0 is as
good as any of the alternatives selected. A more funda-
mental difftculty is created by applying (3.5) to (3.1)
because of the former's inability to realistically re-
°O~--~--~--~----72----L-~3
produce g(x) at x>3 for high densities or thermo-
x dynamic states too near the critical point. Nonetheless,
the subsequent calculations based on (3.5) generally
FIG. 2. g(x) computed from Eqs. (2.12) and (3.5). The PY
results are those of Throop and Bearman. The x-ray diffraction
yield excellent short-range behavior and qualitatively
points are from Mikolaj and Pings for T* = 1.28 and n* = 0.54. correct longer-range behavior.
In order for C3 to be self-consistent, with C1 and C2 ,
it is necessary to base the evaluation of C3 on the
conveniently accomplished by writing down the com- compilations of Levelt. 9 To do this, let us first define
pressibility equationl in terms of reduced variables, viz., the variable
W*= (Z*-1)/1l*. (3.6)
f'"o [g(x) -1]x2dx=C3, (3.1)
Differentiation of (3.6) with respect to n*, yields
where W'*=n*-2[(1/T*) (ap*/an*h.-2Z*+1], (3.7)
(3.2) where
(T*)-I(ap*jan*h.=Z*/ K*. (3.8)
and
Rearranging and combining (3.7) and (3.8) with (3.2)
K*= (a lnn*ja lnp*h •. (3.3)
gives us
The introduction of (3.1) is helpful only if Vex) can
be represented over a somewhat more protracted range
than is afforded by (2.12). The utilization of (3.1) is To complete the calculation of C3 it is necessary to find
especially dangerous for thermodynamic states in the W'* as a function of density and temperature. For a
vicinity of the critical point where the value of the given temperature, plots of TY* are made as a function
integral is comparatively large and is sensitive to the
long-range behavior of g(x). To extend the range of TABLE V. Values of the thermodynamic variable Cs."
Vex) it is necessary to include more terms from (2.9)
or to make use of a series which converges more rapidly, T*
at least in its early terms. The second alternative will
be employed in the next section. For our purposes here, n* 1.3 1.4 1.5
let us be content with adding two more terms to (2.11),
0.050 0.7085 0.5728 0.4719
Vex) =aOl-alx2+a2x4-a3x6+a4x8. (3.4)
0.100 0.9941 0.7183 0.5475
It is supposed that (3.4) will hold for x:::;3. Therefore 0.150 1.4975 0.8954 0.6135
Vex) is represented by 0.200 2.404 1.0596 0.6372
0.250 3.697 1.1212 0.5886
0:::; x:::; 3, 0.300 4.193 0.9594 0.4575
0.325 3.647 0.8021 0.3717
3<x, Vex) =0. (3.5) 0.350 2.821 0.6239 0.2822
Examination of experimental ll and theoreticap-6 results 0.400 1.0731 0.2987 0.1230
0.450 0.3309 0.0917 0.0149
yields the fact that Y(3) is very nearly zero for a
0.500 0.0497 -0.0181 -0.0487
variety of thermodynamic states. It is therefore natural -0.0689 -0.0803
0.550 -0.0481
to impose the boundary condition that there be no 0.575 -0.0711 -0.0820 -0.0887
discontinuity in Vex) at x=3. Notice that (2.5), 0.600 -0.0835 -0.0902 -0.0944
(2.6), (3.1), and the boundary condition at x=3 0.625 -0.0911 -0.0950 -0.0984
provide us with four equations in five unknowns,
leaving one adjustable parameter. Several semiempirical • Based on Ref. 9.

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 IL\OIAL DISTRIBUTION FUNCTION FOR ARGON 4621

of n*. Slopes are then determined to find W'* as a

function of n*. Insertion of W'* into (3.9) along with T* = 1.5
n* and Z* provides the values of C3 given in Table V. n* = 0.25
2
Combination of (3.5) with (2.5), (2.6), and (3.1) • - Eq. (4.2)
along with the conditions that Y(2) and Y(3) equal
( \ • E,.13.5)
zero, permit us to write down five equations in five
unknowns:
(3.10)
g(x)
1
j ~. ".:;,. .:v_".,...., _
where I

and
(3.11)
I x 2 3

I n+2 =
f3 0 exp
(-4>(X))
T* X-4X2ndX, FIG. 3. g(x) computed from Eqs. (3.5) and (4.2). The PY results
are those of Throop and Bearman.

n=O, 1,2,3,4; (3.12)

C2=JI+aod2-ad3+a2J4-aJ5+a.1J6, (3.13) good to poor, depending on the density and tempera-
ture. Calculations for T* = 1.3 are particularly poor at
where distances beyond x= 2.1. As shown in Table VIII,
calculations for T*= 1.5 do not reveal any gross dis-
(3.14) agreement with the PY theory, although there does
appear to be increasing deviation as one goes to higher
and densities. It should perhaps be noted that values for
am, aI, and a2 in Table III do not generally agree with
I n+Z ~'" exp (-;~X)) x-lOx2ndx,
= those in Table VI. This is due primarily to the fact
that we are dealing with two different truncated
n=0,1,2,3,4; (3.15) versions of a series whose terms alternate in sign.
Under these circumstances, the values of the coefficients
C3 = KI+aOlK2-aIK3+a2Kl-a3K4-a3K5+a4K6, (3.16)
are quite sensitive to the number of terms included and
where to the exact set of conditions imposed. The coefficients

f '" {
KI = 0 exp (-4>(X))
-~ -1 } x2dx
and
K n+2= f 3exp (-4>(X))
0 T* XX2nd X,
2
n=O, 1,2,3,4;
am-.fal+ 16a2-64a3+ 256a4=0;
am-9al+81a2-729a3+6561a4=0.
Integrals required for (3.10), (3.13), and (3.16)
are listed in Table II except for K I . Simpson's rule
integration yields 0.52803, 0.45861, and 0.40029 at T*
equal to 1.3, 1.4, and 1.5, respectively, for the latter
integral. Coefficients are solved explicitly as before
and are listed in Table VI. Calculations of g(x) based
on (3.5) and Table VI are enumerated in Tables VII
and VIII for T*= 1.5. Comparison of Table VII with
Table IV reveals that g(x) from Eq. (3.5) corresponds
more closely to the PY theory than does g(x) from
Eq. (2.12) for the region 1.5~x~2.0. In general it is
observed that (3.5) accurately reproduces g(x) up to
about x= 2.1. Beyond X= 2.1, agreement with either
diffraction data or the PY theory ranges from fairly
obtained by applying either Eq. (2.12) or (3.5) should
(3. 17) not be expected to agree well with any later theoretical
evaluation. Instead they should be viewed as coefficients
which will give a "best fit" for the particular truncated
series under consideration.
Examples of the behavior of g(x) based on (3.5)
are shown in Figs. 2 and 3. Comparison can be made
(3.18) with g(x) determined in other ways: (a) x-ray diffrac-
tion, (bi PY-LJ calculations, and (c) Eq. (2.12).
(3.19) Notice that (3.5) agrees very well with the experi-
(3.20) mental results up to about x= 2.1 in Fig. 2. Beyond that
distance, g(x) from (3.5) is still qualitatively correct
in that a second peak and minimum are reproduced
which are present both in the x-ray diffraction and PY
results. In Fig. 3 results are somewhat better at long
range, indicating that the assumptions of the method
are more applicable at lower density and higher tem-
perature.
IV. LONGER-RANGE SOLUTION OF g(x) FROM
A FOURIER SERIES
Widom 8 showed that Y(x) can be given in terms of a
power series in x 2 or by an equivalent representation as a
Fourier integral. Although the Fourier integral is of no
particular use to us here, it is pertinent to write down

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 4622 B R FeE \Y. D.\ V I S

TABLE VI. The constants aOl, ai, a" <13, and a, for Eq. (3.5). four-term Fourier series represents l'(.I:) about as well
as the five-term Taylor series in ,\"2. Equation (4.1)
is then truncated at n=3 and simplified to

T*= 1.3

0.050 0.1461 0.0781 0.0107 -0.0020 -0.0700 + b{cos(27fx/3) J+b 3 cos(7fX) ,

0.100 0.2983 0.2705 0.0705 0.0577 0.0960 3<x, Y(x) =0, (4.2)
0.150 0.4589 0.4691 0.1248 0.0932 0.0685
0.200 0.6135 0.6488 0.1573 0.0681 -0.3890 where it has been assumed that 0:::; x:::; 3 is the applicable
0.250 0.7587 0.8052 0.1672 -0.0176 -0.2706 range.
0.300 0.9076 1.0132 0.2277 0.0276 -1. 2525 The equations obtained by combining (4.2) with
0.325 0.9834 1.1594 0.3043 0.1749 -0.3728 (2.5), (2.6), and (3.1) are
0.350 1.0594 1.3191 0.3968 0.3654 0.8098
0.400 1.2173 1.6456 0.5875 0.7617 3.2822 C1 = Il+~boLo+blLl+b2L2+b3L3, (4.3)
0.450 1.3748 1.9063 0.7134 0.9914 4.6134
0.500 1.5510 2.1524 0.8143 1.1509 5.4504 where
0.550 1.7619 2.4172 0.9131 1.2928 6.1394
0.575 1.8934 2.5736 0.9693 1.3709 6.5072 ( 4.4)
0.600 2.0413 2.7482 1.0315 1.4562 6.9042
0.625 2.2094 2.9448 1.1010 1.5511 7.3441 and
T*= 1.4 (-CP(x))
0.050
0.100
0.1424
0.2992
0.1045
0.3161
0.0257
0.0988
0.0242
0.1131
0.0728
0.4254
Ln=
10
3
exp ~ x-4 [cos(1l7fx/3) Jdx,

n=O, 1,2,3; (4.5)

0.150 0.5602 0.6609 0.2190 0.2640 1.0510
0.200 0.6061 0.7429 0.2457 0.2886 1. 1002 (4.6)
0.250 0.7643 0.9737 0.3304 0.4003 1.5883 where

1'"
0.300 0.9182 1.2109 0.4262 0.5445 2.3092
0.325 0.9931 1.3289 0.4767 0.6259 2.7416
11 = 0
(-cp(X))
exp ~ ;-c-lOdx (4.7)
0.350 1.0623 1.4388 0.5248 0.7058 3.1744
0.400 1.2205 1.6768 0.6259 0.8695 4.0471
0.450 1.3893 1.9114 0.7201 1.0141 4.7888 and
0.500
0.550
0.575
1.5883
1.8244
1.9799
2.1668
2.4528
2.6377
0.8165
0.9202
0.9862
1.1541
1.2990
1.3896
5.4731
6.1589
6.5811
Mn = f exp (-~,~X)) x-lO[cos(nnx/3) Jdx,

0.600 2.1298 2.8120 1.0479 1.4739 6.9722 n=O, 1,2,3; (4.8)

0.625 2.3056 3.0162 1.1199 1.5719 7.4256
C3= Kl+!boNo+blNl+b2N2+b3N3, (4.9)
7'*=1.5 where

1'" { (-cpCX))
0.050 0.1403 0.1257 0.0392 0.0505 0.2282
0.100 0.2951 0.3369 0.1129 0.1416 0.5972 K 1= 0 T* exp }
-1 x2dx (4.10)
0.150 0.4501 O.55~0 0.1919 0.2451 1.0466
0.200 0.6019 0.7751 0.2738 0.3558 1. 5447 and
0.250
0.300
0.325
0.7577
0.9050
O. 9902
1.0020 0.3607
1 220S 0.4475
1 . 3430 0.4964
0.4789
0.6083
0.6818
2.1271
2.7696
3.1392
Nn = f exp (-i~X)) x 2[cos(n7fx/3) ]dx,
0.350 1.1175 1.5164 0.5634 0.7804 3.6254 n=O, 1, 2,3. (4.11)
0.400 1 2279 1.6761 0.6287 0.8821 4.1517
0.450 1.4125 1.9166 0.7201 1.0152 4.8034 The boundary condition that there be no discontinuity
0.500 1.6231 2.1768 0.8156 1.1501 5.4477 at X= 3 provides another equation,
0.550 1.8822 2.4855 0.9262 1.3027 6.1618
0.575 2.0391 2.6694 0.9914 1. 3917 6.5751 (4.12)
0.600 2.2058 2.8629 1.0596 1. 4847 7.0053
0.625 2.3917 3.0781 1.1354 1.5877 7.4812 Equations (4.3), (4.6), (4.9), and (4.12) form a set of
four simultaneous equations in four unknowns which
may be solved explicitly. The additional integrals
the corresponding Fourier series for an even function, required are found in Table IX. The solutions for the
Fourier coefficients are listed in Table X. Values of
( 4.1) g(x) at T*= 1.5 have been computed from the ap-
propriate coefficients and are listed in Tables VII and
As in the case of the Taylor series in X2, a partial sum of VIII. This method for determining g(x) is preferable
the Fourier series will be employed. It turns out that a in that an additional semiempirical condition such as

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 RADIAL DISTRIBUTIO>J FUNCTIO>J FOR ARGON 4623

TABLE VII. g(x) from Eq. (3.5) and from Eq. (4.2) at T*=l.S for x~2.

n*

0.10 0.25 0.40 0.55

x (3.5) (4.2) (3.5) (4.2) (3.5) (4.2) (3.5) (4.2)

0.90 0.013 0.013 0.014 0.015 0.015 0.015 0.017 0.017

0.95 0.290 0.295 0.301 0.312 0.315 0.319 0.352 0.354
1.00 1.058 1.065 1.071 1.086 1.097 1.100 1.199 1.198
1.05 1.728 1.727 1.707 1.704 1.710 1.705 1.827 1.818
1.10 1.982 1.970 1.913 1.885 1.874 1.861 1.952 1.941
1.15 1.955 1.936 1.845 1.802 1. 769 1. 755 1.795 1.788
1.20 1.819 1.798 1.682 1.636 1.580 1.570 1.560 1.561
1.25 1.665 1.645 1.512 1.470 1.394 1.391 1.339 1.351
1.30 1.526 1.510 1.365 1.333 1.238 1.243 1.160 1.181
1.35 1.411 1.401 1.247 1.227 1.117 1.131 1.023 1.053
1.40 1.320 1.315 1.156 1.151 1.027 1.048 0.923 0.960
1.45 1.248 1.249 1.087 1.097 0.962 0.990 0.853 0.896
1.50 1.192 1.200 1.038 1.062 0.918 0.951 0.808 0.854
1.55 1.148 1.163 1.003 1.042 0.891 0.927 0.784 0.829
1.60 1.115 1.136 0.980 1.032 0.878 0.915 0.776 0.818
1.65 1.090 1.116 0.968 1.031 0.876 0.912 0.783 0.818
1. 70 1.072 1.102 0.964 1.035 0.884 0.916 0.801 0.826
1. 75 1.058 1.093 0.966 1.044 0.900 0.926 0.829 0.841
1.80 1.050 1.086 0.974 1.056 0.922 0.939 0.864 0.860
1.85 1.044 1.082 0.987 1.070 0.949 0.954 0.905 0.881
1.90 1.041 1.080 1.003 1.083 0.978 0.970 0.949 0.904
1.95 1.041 1.078 1.022 1.096 1.010 0.987 0.996 0.928
2.00 1.042 1.077 1.042 1.108 1.042 1.003 1.042 0.951

TABLE VIII. g(x) from Eq. (3.5), (4.2), and the py approximation at T*=1.5 for 2<x~3.

n*

0.10 0.25 0.40 0.55

x (3.5) (4.2) pya (3.5) (4.2) pya (3.5) (4.2) pya (3.5) (4.2) pya

2.05 1.044 1.076 1.048 1.063 1.118 1.044 1.073 1.018 1.039 1.086 0.973 1.071
2.10 1.048 1.075 1.050 1.083 1.126 1.055 1.101 1.032 1.053 1.127 0.993 1.086
2.15 1.051 1.073 1.050 1.103 1.131 1.061 1.126 1.043 1.060 1.161 1.010 1.086
2.20 1.055 1.071 1.050 1.120 1.134 1.062 1.147 1.052 1.059 1.189 1.025 1.076
2.25 1.059 1.068 1.048 1.135 1.133 1.060 1.161 1.058 1.054 1.207 1.036 1.059
2.30 1.062 1.065 1.045 1.147 1.130 1.056 1.168 1.062 1.045 1.216 1.045 1.040
2.35 1.064 1.060 1.042 1.155 1.124 1.050 1.168 1.064 1.035 1.214 1.050 1.021
2.40 1.065 1.056 1.039 1.158 1.116 1.044 1.161 1.063 1.025 1.200 1.053 1.004
2.45 1.065 1.050 1.036 1.157 1.107 1.038 1.145 1.060 1.016 1.175 1.053 0.991
2.50 1.064 1.045 1.032 1.151 1.095 1.033 1.122 1.056 1.008 1.139 1.051 0.982
2.55 1.061 1.039 1.029 1.140 1.083 1.028 1.092 1.050 1.002 1.094 1.047 0.976
2.60 1.057 1.033 1.026 1.124 1.070 1.024 1.056 1.044 0.998 1.041 1.041 0.973
2.65 1.052 1.027 1.024 1.105 1.057 1.021 1.017 1.037 0.995 0.984 1.035 0.973
2.70 1.045 1.022 1.022 1.083 1.045 1.019 0.978 1.030 0.994 0.927 1.029 0.976
2.75 1.037 1.017 1.020 1.059 1.034 1.017 0.941 1.023 0.994 0.876 1.022 0.980
3.00 1.004 1.004 1.014 1.004 1.004 1.015 1.004 1.004 1.005 1.004 1.004 1.008

• Reference 6.

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 4624 BRUCE W. DAVIS

TABLE IX. Numerical values of integrals of the type, agreement with the {'ID computations than (3.S).
X~ray diffraction points are in good agreement with
J3 exp (;*4 (X~12_X-6») xm cos (mrx/3) dx. both the .l\lD curve and Eq. (4.2) even though they
o correspond to a somewhat lower density.
It has been found that values of g(x) based on (4.2)
n

T* 2 3 TABLE X. The constants !b o, b" b" and b3 for Eq. (4.2).

+0.09574 -0.21067 n* b3
-10 -0.15020
1.3 -4 +0.11861 -0.37899 -0.31721
+2 -5.6513 +0.78674 -0.66599 T*= 1.3

-10 +0.09431 -0.14597 -0.20651 0.050 0.0835 0.1129 0.0572 0.0278

1.4 -4 +0.11414 -0.36671 -0.30570 0.100 0.2222 0.3053 0.2303 0.1472
+2 -5.6560 +0.83613 -0.64339 0.150 0.4331 0.5841 0.4839 0.3330
0.200 0.7720 1.0114 0.8757 0.6364
-10 +0.09336 -0.14262 -0.20349 0.250 1.2315 1. 5780 1.3971 1.0506
1.5 -4 +0.11059 -0.35659 -0.29645 0.300 1.4413 1. 8561 1. 6600 1.2452
+2 -5.6595 +0.87753 -0.62509 0.325 1.2955 1.7044 1.5284 1. 1195
0.350 1. 0610 1.4497 1.3034 0.9148
0.400 0.5627 0.9065 0.8203 0.4765
Y(2) = 0 does not have to be imposed to solve the 0.450 0.3797 0.7276 0.6612 0.3133
simultaneous equations. Comparison of the Fourier 0.500 0.3453 0.7230 0.6530 0.2754
series method with the PY and HNC theories, experi~ 0.550 0.3766 0.7994 0.7104 0.2876
0.575 0.3656 0.7842 0.6938 0.2752
mental data, and values due to Eq. (3.5) are made in
0.600 0.2626 0.6006 0.5411 0.2031
Figs. 3-5. 0.625 0.1398 0.3803 0.3579 0.1174
Further comparisons are made in Fig. 6. The solid
line represents a smooth curve drawn through "exact" T*= 1.4
molecular dynamics (MD) results7 for x:=; 2.4. These 0.050 0.0668 0.0963 0.0535 0.0240
data are exact in the sense that g(x) is given to within 0.100 0.1629 0.2406 0.1857 0.1079
about 1% for a system of particles having only pairwise 0.150 0.2684 0.3956 0.3299 0.2027
LJ interactions. Calculations of this kind have an 0.200 0.3712 0.5485 0.4736 0.2963
advantage in that no additional error accrues from 0.250 0.4435 0.6672 0.5878 0.3641
introduction of the PY, HNC, or some other approxi~ 0.300 0.4443 0.7024 0.6264 0.3683
mation. Cl , C2 , and Ca obtained by interpolation be~ 0.325 0.4198 0.6906 0.6183 0.3475
tween values given in Tables I and V were used to 0.350 0.3866 0.6673 0.5993 0.3187
0.400 0.3352 0.6413 0.5770 0.2710
determine the coefficients m Eqs. (3.5) and (4.2).
0.450 0.3223 0.6605 0.5912 0.2530
X~ray diffraction data ll are also shown for T*= 1.36
0.500 0.3470 0.7275 0.6424 0.2618
at n* = 0.46. It is clear that (4.2) gives better over~all 0.550 0.3990 0.8318 0.7204 0.2876
0.575 0.4355 0.9003 0.7714 0.3066
0.600 0.4788 0.9801 0.8303 0.3290
0.625 0.5268 1. 0676 0.8945 0.3538
T* = 1.3
n* = 0.55 T*= 1.5
2
- Eq. (4.2) 0.050 0.0560 0.0856 0.0515 0.0219
o py 0.100 0.1291 0.2030 0.1600 0.0861
• X-ray Diffraction 0.150 0.1998 0.3179 0.2676 0.1494
g(x)
0.200 0.2568 0.4170 0.3625 0.2023
0.250 0.2921 0.4916 0.4341 0.2346
0.300 0.2988 0.5313 0.4735 0.2410
0.325 0.2989 0.5494 0.4901 0.2397
0.350 0.3100 0.5879 0.5225 0.2445
0.400 0.2948 0.5935 0.5271 0.2285
0.450 0.3161 0.6543 0.5746 0.2364
0.500 0.3573 0.7418 0.6408 0.2564
0.550 0.4211 0.8634 0.7316 0.2893
0.575 0.4628 0.9403 0.7884 0.3109
FIG. 4. g(x) computed from Eq. (4.2). The PY results are 0.600 0.5077 1.0225 0.8487 0.3339
those of Throop and Bearman. The x-ray diffraction points are 0.625 0.5586 1.1149 0.9163 0.3600
from M ikolaj and Pings for T* = 1.28 and n* = 0.54.

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 RADIAL DISTRIBUTION FUNCTION FOR .\RGON 4625

behave rather poorly in the range 1.6~x~3 for states

near the critical point. For example at T* = 1.3 and
n*=O.325, g(x) is much too large for 1.6~x~3, in fact
reaching an unrealistic value of 1.96 at x= 2.15.
Equation (3.5) does not give any basic improvement,
yielding a maximum value of g(x) = 1.90 at x= 2.65.
In general it appears that (4.2) affords a slightly
better method of reproducing g(x) than either (2.12)
or (3.5). Since (4.2) has not been forced to fit ap-
proximately at x= 2, the compilations of g(x) based on
it can more nearly be regarded as ad hoc calculations
produced solely from thermodynamic data and the LJ
potential.
v. DISCUSSION
As far as the author is aware, this is the first suc-
cessful calculation of g(x) only from thermodynamic
data and a model potential. All three variations of the
method have been shown to be suitable for reproducing
accurate values of g(x) at x~ 1.5. For thermodynamic
states not too near the critical point the three variations
differ by only a few percent. The third method gives a
better over-all fit than the second method for the range
0~x~3 although the latter is sometimes superior for
1.5 ~ x~ 2. It should be noted that the general method
need not be limited to the two types of series defined
by Eqs. (2.9) and (4.1). There is a reasonable chance
that some other series for Y(x) which converges more
rapidly than (2.9) or (4.1) in its early terms will
permit a more complete solution.
In a still different approach one might calculate one
or two of the early terms in (2.9) or (4.1) theoretically,
thereby permitting addition of extra terms without
imposing semiempirical conditions at one or more
T* = 1.5
2 n* = 0.60
• Eq. (4.2)
o py
v HNC
g(x)
0:0--~----7-------~2----~--~3
x 9 J. M. H. Levelt, Physica 26, 361 (1960).
FIG. 5. g(x) computed from Eq. (4.2). The PY results are
those of Throop and Bearman. The HNC results are those of
De Boer, Van Leeuwen, and Groeneveld. The smooth curves
are drawn through the PY results and the results of Eq. (4.2).
T* = 1.36
2.0 n* = 0.50
MD
Eq. (3.5)
Eq. (4.2)
1.5
o X-ray Diffraction
g (x) ........
1.0
0.5
2 3
x
FIG. 6. g(x) computed by molecular-dynamics method. The
smooth curve is drawn through Verlet's molecular-dynamics data.
The x-ray diffraction points are from Mikolaj and Pings for
T* = 1.36 and n' = 0.46.
points in the Y(x) curve. The coefficients of the non-
theoretical terms would then assume values which
conform to a best fit for the truncated series at hand.
Such a technique would be a hybrid, in the sense that it
relied partly on theoretical means and partly on thermo-
dynamic data to construct the radial distribution
function.
* This work was supported in part by the Petroleum Research
Fund of the American Chemical Society and in part by the Army
Research Office, Durham. The author is grateful for this support.
1 T. L. Hill, Statistical Mechanics (McGraw-Hill, New York,
1956), pp. 189, 190, 236.
2 W. G. Hoover, A. C. Holt, D. R. Shortie, and S. G. Gray,
J. Chern. Phys. 52,1782 (1970).
3 M. Klein and M. S. Green, J. Chern. Phys. 39, 1367 (1963).
4 J. De Boer, J. M. J. Van Leeuwen, and J. Groeneveld, Physica
30, 2265 (1964).
6 A. A. Khan, Phys. Rev. 134, A367 (1964).
6 G. J. Throop and R. J. Bearman, Physica 32, 1298 (1966).
7L. Verlet, Phys. Rev. 159,98 (1967); Phys. Rev. 165, 201
(1968) .
8 B. Widom, J. Chern. Phys. 39, 2808 (1963).
10 B. Wid om, J. Chern. Phys. 42, 1128 (1965).
11 P. G. Mikolaj and C. J. Pings, J. Chern. Phys. 46, 1401
(1967) .
12 The parameters used for reduction of variables are the same
as those of Ref. 6, i.e., elk = 119.8°K and To= 3.405 A.

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