Phase behaviour and thermodynamic anomalies of core-softened fluids

TL;DR

This study uses advanced simulations to explore phase behavior and anomalies in core-softened fluids, revealing different origins of thermodynamic anomalies in two models and confirming a second critical point in one.

Contribution

It provides detailed phase diagrams and clarifies the origins of thermodynamic anomalies in two distinct core-softened fluid models.

Findings

The shoulder model's anomalies are due to quasi-continuous freezing, not a liquid-liquid critical point.

The ramp model exhibits a stable liquid-liquid critical point at high pressure and low temperature.

Thermodynamic anomalies in the ramp model are genuine, not caused by a new phase.

Abstract

We report extensive simulation studies of phase behaviour in single component systems of particles interacting via a core-softened interparticle potential. Two recently proposed examples of such potentials are considered; one in which the hard core exhibits a shoulder, (Sadr-Lahijany et al, Phys. Rev. Lett. 81, 4895 (1998)) and the other in which the softening takes the form of a linear ramp (Jagla, Phys. Rev. E63, 061501 (2001)). Using a combination of state-of-the-art Monte Carlo methods, we obtain the gas, liquid and solid phase behaviour of the shoulder model in two dimensions. We then focus on the thermodynamic anomalies of the liquid phase, namely maxima in the density and compressibility as a function of temperature. Analysis of the finite-size behaviour of these maxima suggests that, rather than stemming from a metastable liquid-liquid critical point, as previously supposed, they are actually induced by the quasi-continuous nature of the two dimensional freezing transition. For the ramp model in three dimensions, we confirm the existence of a stable liquid-liquid ("second") critical point occurring at higher pressure and lower temperature than the liquid-gas critical point. Both these critical points and portions of their associated coexistence curves are located to high precision. In contrast to the shoulder model, the observed thermodynamic anomalies of this model are found to be authentic, i.e. they are not engendered by an incipient new phase. We trace the locus of density and compressibility maxima, the former of which appears to converge on the second critical point.