Exact values of two cluster integrals in the fifth virial coefficient for hard spheres

1968 ◽  
Vol 27 (6) ◽  
pp. 378-379 ◽  
Author(s):  
S. Kim ◽  
D. Henderson

The fifth virial coefficient of a fluid of hard spheres is a sum of 238 irreducible cluster integrals of 10 different types. The values of 5 of these types (152 integrals) are obtained analytically, the contributions of a further 4 types (85 integrals) are obtained by a com­bination of analytical and numerical integration, and 1 integral is calculated by an approximation. The result is E = (0·1093 ± 0·0007) b 4 , b = 2/3 πN A σ 3 , where σ is the diameter of a sphere. A combination of the values of 237 of the cluster integrals obtained in this paper with the value of one integral obtained independently by Katsura & Abe from a Monte Carlo calculation yields E = (0·1101 ± 0·0003) b 4 .


It is shown how to evaluate the two-body, and three-body cluster integrals, ɳ 3 , ɳ * 3 , β 3 , β * 3 (equations (1.1) to (1.4)) for the hard-sphere, square-well and Lennard-Jones ( v :½ v ) potentials; the three-body potential used is the dipole-dipole-dipole potential of Axilrod & Teller. Explicit expressions are presented for the integrals ɳ * 3 , β * 3 using the above potentials; in the case of the first integral, its values for both small and large values of the separation distance are also given, for the Lennard-Jones ( v :½ v ) potential. Similar considerations have been carried out for ɳ 3 and β 3 , except that explicit expressions for the hard-sphere, and square-well potentials are not given, since these had been done before by other authors. The intermediate expressions for the four cluster integrals, are in terms of single integrals, and such expressions are valid for any continuous potential. Numerical results based on some of the expressions in this paper are compared with the results of numerical evaluation of the above integrals by other authors, and the agreement is seen to be good. Making use of the Mikolaj-Pings relation, the above results are used to obtain relationships between the second virial coefficient, and X-ray scattering data, as well as a means of deducing the pair potential at large separations, directly from a knowledge of X-ray scattering data, and the second virial coefficient.


1994 ◽  
Vol 06 (05a) ◽  
pp. 947-975 ◽  
Author(s):  
M. D. PENROSE ◽  
O. PENROSE ◽  
G. STELL

For a 3-dimensional system of hard spheres of diameter D and mass m with an added attractive square-well two-body interaction of width a and depth ε, let BD, a denote the quantum second virial coefficient. Let BD denote the quantum second virial coefficient for hard spheres of diameter D without the added attractive interaction. We show that in the limit a → 0 at constant α: = ℰma2/(2ħ2) with α < π2/8, [Formula: see text] The result is true equally for Boltzmann, Bose and Fermi statistics. The method of proof uses the mathematics of Brownian motion. For α > π2/8, we argue that the gaseous phase disappears in the limit a → 0, so that the second virial coefficient becomes irrelevant.


1985 ◽  
Vol 55 (3) ◽  
pp. 599-610 ◽  
Author(s):  
G.S. Rushbrooke ◽  
R.G. Shrubsall

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