Melting upon cooling and freezing upon heating: fluid–solid phase diagram for Švejk–Hašek model of dimerizing hard spheres

Abstract

A simple model of dimerizing hard spheres with highly nontrivial fluid–solid phase behavior is proposed and 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 temperatures lower than those of the solid branch. This unusual behavior 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 behavior.