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.

Statistical entropy and clustering in absence of attractive terms in the interparticle potential

Recently a new intriguing class of systems has been introduced, the so-called generalized exponential models, which exhibit clustering phenomena even if the attractive term is missing in their interaction potential. This model is characterized by a index n which tunes the repulsive penetrability of the potential. This family of potentials can represent the effective interactions for a large number of soft matter systems. In this paper we study the structural and thermodynamic properties in the fluid regime of the generalized exponential model with a value of index n suggested by Mladek et al. [B. M. Mladek, G. Kahl, and C. N. Likos, Phys. Rev. Lett. (2008)] to fit the effective potential of a typical amphiphilic dendrimers. We use the conventional approach of the liquid state theory based on the hypernetted chain closure of the Ornstein-Zernike equation together with some Monte Carlo numerical simulations. Moreover, we try to detect qualitatively the freezing line exploiting the predictive properties of a one-phase rule based on the expansion of the statistical entropy

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

Residual Multiparticle Entropy for a Fractal Fluid of Hard Spheres

The residual multiparticle entropy (RMPE) of a fluid is defined as the difference, $\Delta s$, between the excess entropy per particle (relative to an ideal gas with the same temperature and density), $s_\text{ex}$, and the pair-correlation contribution, $s_2$. Thus, the RMPE represents the net contribution to $s_\text{ex}$ due to spatial correlations involving three, four, or more particles. A heuristic `ordering' criterion identifies the vanishing of the RMPE as an underlying signature of an impending structural or thermodynamic transition of the system from a less ordered to a more spatially organized condition (freezing is a typical example). Regardless of this, the knowledge of the RMPE is important to assess the impact of non-pair multiparticle correlations on the entropy of the fluid. Recently, an accurate and simple proposal for the thermodynamic and structural properties of a hard-sphere fluid in fractional dimension $1<d<3$ has been proposed [Santos, A.; L\'opez de Haro, M. \emph{Phys. Rev. E} \textbf{2016}, \emph{93}, 062126]. The aim of this work is to use this approach to evaluate the RMPE as a function of both $d$ and the packing fraction $\phi$. It is observed that, for any given dimensionality $d$, the RMPE takes negative values for small densities, reaches a negative minimum $\Delta s_{\text{min}}$ at a packing fraction $\phi_{\text{min}}$, and then rapidly increases, becoming positive beyond a certain packing fraction $\phi_0$. Interestingly, while both $\phi_{\text{min}}$ and $\phi_0$ monotonically decrease as dimensionality increases, the value of $\Delta s_{\text{min}}$ exhibits a nonmonotonic behavior, reaching an absolute minimum at a fractional dimensionality $d\simeq 2.38$. A plot of the scaled RMPE $\Delta s/|\Delta s_{\text{min}}|$ shows a quasiuniversal behavior in the region $-0.14\lesssim\phi-\phi_0\lesssim 0.02$.Comment: 10 pages, 3 figures; v2: minor change