Generic maximum-valence model for fluid polyamorphism.

Abstract

Recently, a maximal-valence model has been proposed to model a liquid-liquid phase transition induced by polymerization in sulfur. In this paper we present a simple generic model to describe liquid polyamorphism in single-component fluids using a maximum-valence approach for any arbitrary coordination number. The model contains three types of interactions: (i) atoms attract each other by van der Waals forces that generate a liquid-gas transition at low pressures, (ii) atoms may form covalent bonds that induce association, and (iii) additional repulsive forces between atoms with maximal valence and atoms with any valence. This additional repulsion generates liquid-liquid phase separation and the region of the negative heat expansion coefficient (density anomaly) on a P-T phase diagram. We show the existence of liquid-liquid phase transitions for dimerization, polymerization, gelation, and network formation for corresponding coordination numbers z=1,2,...,6 and discuss the limits of this generic model for producing fluid polyamorphism.