Universal behavior of soft-core fluids near the threshold of thermodynamic stability

TL;DR

This study combines liquid-state theories and Monte Carlo simulations to analyze how soft-core fluids behave near the point where they become thermodynamically unstable, revealing a universal pattern in their phase behavior.

Contribution

It demonstrates a universal behavior in soft-core fluids approaching Ruelle instability, supported by theoretical and simulation evidence across various potential forms.

Findings

Widening of the liquid-vapor binodal near instability

Vanishing vapor density coexists with diverging liquid density

Universal pathway to Ruelle instability identified

Abstract

We study, by using liquid-state theories and Monte Carlo simulation, the behavior of systems of classical particles interacting through a finite pair repulsion supplemented with a longer range attraction. Any such potential can be driven Ruelle-unstable by increasing the attraction at the expense of repulsion, until the thermodynamic limit is lost. By examining several potential forms, we find that all systems exhibit a qualitatively similar behavior in the fluid phase as the threshold of thermodynamic stability is approached (and possibly surpassed). The general feature underlying the approach to Ruelle instability is a pronounced widening of the liquid-vapor binodal (and spinodal) line at low temperatures, to such an extent that at the stability threshold a vanishing-density vapor would coexist with a diverging-density liquid. We attempt to rationalize the universal pathway to Ruelle instability in soft-core fluids by appealing to a heuristic argument.