Liquid-liquid critical point: an analytical approach

Abstract

Theoretical simulations and experimental studies have showed that many systems (like liquid metals) can exhibit two phase transitions: gas-liquid and liquid-liquid. Consequently the fluid phase of these systems presents two critical points, namely the usual gas-liquid (G-L) critical point and the liquid-liquid critical point that results from a phase transition between two liquids of different densities: a low density liquid (LDL) and a high density liquid (HDL). The van der Waals theory for simple fluids [Phys. Rev. E 50, 2913 (1994)] is based on taking a system with purely repulsive forces as a reference, is able to describe two stable first-order phase transitions between fluids of different densities. The particles in our system interact via a total pair potential, which splits into a repulsive VR and a density-dependent attractive VA part.