Structural behavior of fluids from the vapor and liquid region to the supercritical phase.

Abstract

A metric (χ) is introduced to quantify the relative proportion of particles having a specified number of near neighbors that are characteristic of liquid-phase properties. It can be used as a simple alternative to other methods for the investigation of some aspects of percolation behavior. Values of χ are obtained from molecular-dynamics simulations spanning the heterogeneous vapor and liquid region and the supercritical phase of the Lennard-Jones fluid. The supercritical phase can be delineated into regions of different structural properties. At different isochoric subcritical conditions, the temperature versus χ behavior shows evidence of inflections, which are associated with the onset of transitions from the vapor and liquid region to the supercritical phase. The analysis suggests a phenomenological requirement for the critical point in terms of a near-equal proportion of near neighbors with gaslike and liquidlike characteristics.