Three-dimensional patchy lattice model for empty fluids

TL;DR

This study explores a 3D patchy lattice model with specific patch interactions, revealing reentrant liquid-vapor phase behavior and a closed-loop phase diagram, challenging previous assumptions about universal thresholds.

Contribution

It introduces a novel 3D lattice model with unique phase diagram features, including reentrant behavior and a closed-loop, expanding understanding of patchy particle systems.

Findings

Reentrant liquid-vapor phase equilibria for r < 1/3.

Existence of a closed-loop with a lower critical point.

Reentrant behavior occurs within an equilibrium phase region.

Abstract

The phase diagram of a simple model with two patches of type A and ten patches of type B (2A10B) on the face centred cubic lattice has been calculated by simulations and theory. Assuming that there is no interaction between the B patches the behavior of the system can be described in terms of the ratio of the AB and AA interactions, r. Our results show that, similarly to what happens for related off-lattice and two-dimensional lattice models, the liquid-vapor phase equilibria exhibits reentrant behavior for some values of the interaction parameters. However, for the model studied here the liquid-vapor phase equilibria occurs for values of r lower than 1/3, a threshold value which was previously thought to be universal for 2AnB models. In addition, the theory predicts that below r = 1/3 (and above a new condensation threshold which is < 1/3) the reentrant liquid-vapor equilibria is so extreme that it exhibits a closed loop with a lower critical point, a very unusual behavior in single-component systems. An order-disorder transition is also observed at higher densities than the liquid-vapor equilibria, which shows that the liquid-vapor reentrancy occurs in an equilibrium region of the phase diagram. These findings may have implications in the understanding of the condensation of dipolar hard spheres given the analogy between that system and the 2AnB models considered here.