Melting upon cooling and freezing upon heating: Fluid-solid phase diagram for Svejk-Hasek model of dimerizing hard spheres

TL;DR

This paper introduces a model of dimerizing hard spheres exhibiting unusual fluid-solid phase behavior, where melting occurs upon cooling and freezing upon heating, due to temperature-dependent excluded volume effects.

Contribution

The study applies resummed thermodynamic perturbation theory to analyze a novel fluid-solid phase diagram with unconventional temperature-dependent phase transitions.

Findings

Fluid branch of coexistence curve at lower temperatures than solid branch

Unusual melting and freezing behavior related to temperature-dependent excluded volume

Potential applicability to other models with combined short-range attraction and repulsion

Abstract

A simple model of dimerizing hard spheres with highly nontrivial fluid-solid phase behaviour is proposed. The model is studied using the recently proposed resummed thermodynamic perturbation theory for central force (RTPT-CF) associating potentials. The phase diagram has the fluid branch of the fluid-solid coexistence curve located at a temperatures lower than those of the solid branch. This unusual behaviour is related to the strong dependence of the system excluded volume on the temperature, which for the model at hand decreases with increasing temperature. This effect can be also seen for a wide family of fluid models with an effective interaction that combines short range attraction and repulsion at a larger distance. We expect that for sufficiently high repulsive barrier, such systems may show similar phase behaviour.