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

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.Comment: 21 pages, 7 figures, in press on Phys. Rev.

A probabilistic model for the equilibration of an ideal gas

I present a generalization of the Ehrenfest urn model that is aimed at simulating the approach to equilibrium in a dilute gas. The present model differs from the original one in two respects: 1) the two boxes have different volumes and are divided into identical cells with either multiple or single occupancy; 2) particles, which carry also a velocity vector, are subjected to random, but elastic, collisions, both mutual and against the container walls. I show, both analytically and numerically, that the number and energy of particles in a given urn evolve eventually to an equilibrium probability density $W$ which, depending on cell occupancy, is binomial or hypergeometric in the particle number and beta-like in the energy. Moreover, the Boltzmann entropy $\ln W$ takes precisely the same form as the thermodynamic entropy of an ideal gas. This exercise can be useful for pedagogical purposes in that it provides, although in an extremely simplified case, a probabilistic justification for the maximum-entropy principle.Comment: 9 pages, 2 figure

Probing the existence of phase transitions in one-dimensional fluids of penetrable particles

Phase transitions in one-dimensional classical fluids are usually ruled out by making appeal to van Hove's theorem. A way to circumvent the conclusions of the theorem is to consider an interparticle potential that is everywhere bounded. Such is the case of, {\it e.g.}, the generalized exponential model of index 4 (GEM-4 potential), which in three dimensions gives a reasonable description of the effective repulsion between flexible dendrimers in a solution. An extensive Monte Carlo simulation of the one-dimensional GEM-4 model [S. Prestipino, {\em Phys. Rev. E} {\bf 90}, 042306 (2014)] has recently provided evidence of an infinite sequence of low-temperature cluster phases, however also suggesting that upon pushing the simulation forward what seemed a true transition may eventually prove to be only a sharp crossover. We hereby investigate this problem theoretically, by three different and increasingly sophisticated approaches ({\it i.e.}, a mean-field theory, the transfer matrix of a lattice model of clusters, and the exact treatment of a system of point clusters in the continuum), to conclude that the alleged transitions of the one-dimensional GEM4 system are likely just crossovers.Comment: 18 pages, 9 figure

Can one have preroughening of vicinal surfaces?

We discuss the possibility that, besides roughening, a vicinal surface could display preroughening (PR), and consider the possible mechanisms for its promotion. Within the framework of a terrace-step-kink model, it turns out that a PR transition is possible, and could be induced by a short-range repulsion between parallel kinks along the same step or on adjacent steps, or even by some kind of extended range step-step repulsion. We discuss the possible relevance of this phenomenon to the anomalous roughening behaviour recently reported for Ag(115).Comment: 9 pages, 3 postscript figures, submitted to Surface Scienc

Hexatic phase and water-like anomalies in a two-dimensional fluid of particles with a weakly softened core

We study a two-dimensional fluid of particles interacting through a spherically-symmetric and marginally soft two-body repulsion. This model can exist in three different crystal phases, one of them with square symmetry and the other two triangular. We show that, while the triangular solids first melt into a hexatic fluid, the square solid is directly transformed on heating into an isotropic fluid through a first-order transition, with no intermediate tetratic phase. In the low-pressure triangular and square crystals melting is reentrant provided the temperature is not too low, but without the necessity of two competing nearest-neighbor distances over a range of pressures. A whole spectrum of water-like fluid anomalies completes the picture for this model potential.Comment: 26 pages, 14 figures; printed article available at http://link.aip.org/link/?jcp/137/10450