On the choice of the effective diameter in the high-temperature expansion for the Lennard–Jones fluid

Abstract

A third-order perturbation theory, within the framework of the high temperature expansion, with the perturbation terms obtained from computer simulation, is used to test the performance of several prescriptions proposed in the literature to obtain the effective hard-sphere diameter for the Lennard–Jones fluid. It is found that the classical Barker–Henderson prescription provides, on the whole, the best accuracy as compared with the available simulation data for the excess energy, the equation of state and the liquid-vapour coexistence densities.

GRAPHICAL ABSTRACT

Keywords:

• Perturbation theory
• Monte Carlo simulation
• Lennard–Jones potential
• effective hard-sphere diameter

Disclosure statement

No potential conflict of interest was reported by the author(s).

Notes

1 We will not give here the cited expression, but the interested reader can find a detailed account in Ref. [1, pp. 116–121].