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

A metric (chi) 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 chi 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 chi 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.