Phase behavior and thermodynamic anomalies of core-softened fluids.

Abstract

We report extensive simulation studies of phase behavior 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. E 63, 061501 (2001)]. Using a combination of state-of-the-art Monte Carlo methods, we obtain the gas, liquid, and solid phase behavior 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 behavior of these maxima suggests that, rather than stemming from a metastable liquid-liquid critical point, as previously supposed, they are actually induced by the quasicontinuous 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 terminate close to the second critical point.