Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids

Abstract

The different roles the attractive and repulsive forces play in forming the equilibrium structure of a Lennard‐Jones liquid are discussed. It is found that the effects of these forces are most easily separated by considering the structure factor (or equivalently, the Fourier transform of the pair‐correlation function) rather than the pair‐correlation function itself. At intermediate and large wave vectors, the repulsive forces dominate the quantitative behavior of the liquid structure factor. The attractions are manifested primarily in the small wave vector part of the structure factor; but this effect decreases as the density increases and is almost negligible at reduced densities higher than 0.65. These conclusions are established by considering the structure factor of a hypothetical reference system in which the intermolecular forces are entirely repulsive and identical to the repulsive forces in a Lennard‐Jones fluid. This reference system structure factor is calculated with the aid of a simple but accurate approximation described herein. The conclusions lead to a very simple prescription for calculating the radial distribution function of dense liquids which is more accurate than that obtained by any previously reported theory. The thermodynamic ramifications of the conclusions are presented in the form of calculations of the free energy, the internal energy (from the energy equation), and the pressure (from the virial equation). The implications of our conclusions to perturbation theories for liquids and to the interpretation of x‐ray scattering experiments are discussed.