Liquid-Liquid Phase Transition for an Attractive Isotropic Potential with Wide Repulsive Range

TL;DR

This study explores how the phase diagram of an isotropic system with a soft-core squared attractive potential changes with varying parameters, revealing conditions for two distinct liquid-liquid critical points using an integral equation approach.

Contribution

It extends previous analyses by examining large soft-core ranges and demonstrates the existence of two well-separated fluid-fluid critical points under specific potential parameter conditions.

Findings

Two fluid-fluid critical points are identified with large soft-core ranges.

The critical points' temperature and density depend on potential parameters.

A simple relation between potential parameters is satisfied for large soft-core ranges.

Abstract

Recent experimental and theoretical results have shown the existence of a liquid-liquid phase transition in isotropic systems, such as biological solutions and colloids, whose interaction can be represented via an effective potential with a repulsive soft-core and an attractive part. We investigate how the phase diagram of a schematic general isotropic system, interacting via a soft-core squared attractive potential, changes by varying the parameters of the potential. It has been shown that this potential has a phase diagram with a liquid-liquid phase transition in addition to the standard gas-liquid phase transition and that, for a short-range soft-core, the phase diagram resulting from molecular dynamics simulations can be interpreted through a modified van der Waals equation. Here we consider the case of soft-core ranges comparable with or larger than the hard-core diameter. Because an analysis using molecular dynamics simulations of such systems or potentials is too time-demanding, we adopt an integral equation approach in the hypernetted-chain approximation. Thus we can estimate how the temperature and density of both critical points depend on the potential's parameters for large soft-core ranges. The present results confirm and extend our previous analysis, showing that this potential has two fluid-fluid critical points that are well separated in temperature and in density only if there is a balance between the attractive and repulsive part of the potential. We find that for large soft-core ranges our results satisfy a simple relation between the potential's parameters.