Anomalous phase behavior of a soft-repulsive potential with a strictly monotonic force

TL;DR

This study explores the complex phase behavior of particles interacting via a strictly convex soft-repulsive potential, revealing multiple re-entrant fluid-solid transitions, diverse solid polymorphs, and water-like anomalies despite the isotropic interactions.

Contribution

It demonstrates that a strictly convex soft-repulsive potential can produce rich phase phenomena, including multiple re-entrant transitions and complex crystal structures, expanding understanding beyond previous models.

Findings

Multiple re-entrant fluid-solid coexistence regions

Presence of diverse solid polymorphs including non-Bravais lattices

Water-like anomalies observed in the system

Abstract

We study the phase behavior of a classical system of particles interacting through a strictly convex soft-repulsive potential which, at variance with the pairwise softened repulsions considered so far in the literature, lacks a region of downward or zero curvature. Nonetheless, such interaction is characterized by two length scales, owing to the presence of a range of interparticle distances where the repulsive force increases, for decreasing distance, much more slowly than in the adjacent regions. We investigate, using extensive Monte Carlo simulations combined with accurate free-energy calculations, the phase diagram of the system under consideration. We find that the model exhibits a fluid-solid coexistence line with multiple re-entrant regions, an extremely rich solid polymorphism with solid-solid transitions, and water-like anomalies. In spite of the isotropic nature of the interparticle potential, we find that, among the crystal structures in which the system can exist, there are also a number of non-Bravais lattices, such as cI16 and diamond.