A perturbation theory of classical equilibrium fluids

Abstract

A new perturbation theory which is reliable over a wide fluid region is presented. The new theory reduces to the theory of Weeks, Chandler, and Anderson at densities near or below the triple point density of a simple fluid but it can also accurately predict thermodynamic properties at higher densities near the freezing line of the fluid. This is done by employing an optimized reference potential whose repulsive range decreases with increase in density. Thermodynamic properties for Lennard‐Jones, exponential‐6, and inverse nth‐power (n=12, 9, 6, and 4) potentials have been calculated from the new theory. Comparison of the calculated data with available Monte Carlo simulations and additional simulations carried out in this work shows that the theory gives excellent thermodynamic results for these systems. The present theory also gives a physically reasonable hard‐sphere diameter over the entire fluid range.