Entropy scaling close to criticality: From simple to metallic systems.

Abstract

Entropy has recently drawn considerable interest both as a marker to detect the onset of phase transitions and as a reaction coordinate, or collective variable, to span phase transition pathways. We focus here on the behavior of entropy along the vapor-liquid phase coexistence and identify how the difference in entropy between the two coexisting phases vary in ideal and metallic systems along the coexistence curve. Using flat-histogram simulations, we determine the thermodynamic conditions of coexistence, critical parameters, including the critical entropy, and entropies along the binodal. We then apply our analysis to a series of systems that increasingly depart from ideality and adopt a metal-like character, through the gradual onset of the Friedel oscillation in an effective pair potential, and for a series of transition metals modeled with a many-body embedded-atoms force field. Projections of the phase boundary on the entropy-pressure and entropy-temperature planes exhibit two qualitatively different behaviors. While all systems modeled with an effective pair potential lead to an ideal-like behavior, the onset of many-body effects results in a departure from ideality and a markedly greater exponent for the variation of the entropy of vaporization with temperature away from the critical temperature.