Two-dimensional crystals of classical particles are very peculiar in that melting may occur in two steps, in a continuous fashion, via an intermediate hexatic fluid phase exhibiting quasi-long-range orientational order. On the other hand, three-dimen
sional spheres repelling each other through a fast-decaying bounded potential of generalized-exponential shape (GEM4 potential) can undergo freezing into cluster crystals, allowing for more that one particle per lattice site. We hereby study the combined effect of low spatial dimensionality and extreme potential softness, by investigating the phase behavior of the two-dimensional (2D) GEM4 system. Using a combination of density-functional theory and numerical free-energy calculations, we show that the 2D GEM4 system displays one ordinary and several cluster triangular-crystal phases, and that only the ordinary crystal first melts into a hexatic phase. Upon heating, the difference between the various cluster crystals fades away, eventually leaving a single undifferentiated cluster phase with a pressure-modulated site occupancy.
Phase transitions are uncommon among homogenous one-dimensional fluids of classical particles owing to a general non-existence result due to van Hove. A way to circumvent van Hoves theorem is to consider an interparticle potential that is finite ever
ywhere. Of this type is the generalized exponential model of index 4 (GEM4 potential), a model interaction which in three dimensions provides an accurate description of the effective pair repulsion between dissolved soft macromolecules (e.g., flexible dendrimers). Using specialized free-energy methods, I reconstruct the equilibrium phase diagram of the one-dimensional GEM4 system, showing that, apart from the usual fluid phase at low densities, it consists of an endless sequence of {em cluster fluid phases} of increasing pressure, having a sharp crystal appearance for low temperatures. The coexistence line between successive phases in the sequence invariably terminates at a critical point. Focussing on the first of such transitions, I show that the growth of the 2-cluster phase from the metastable ordinary fluid is extremely slow, even for large supersaturations. Finally, I clarify the apparent paradox of the observation of an activation barrier to nucleation in a system where, due to the dimensionality of the hosting space, the critical radius is expected to vanish.
Pair potentials that are bounded at the origin provide an accurate description of the effective interaction for many systems of dissolved soft macromolecules (e.g., flexible dendrimers). Using numerical free-energy calculations, we reconstruct the eq
uilibrium phase diagram of a system of particles interacting through a potential that brings together a Gaussian repulsion with a much weaker Gaussian attraction, close to the thermodynamic stability threshold. Compared to the purely-repulsive model, only the reentrant branch of the melting line survives, since for lower densities solidification is overridden by liquid-vapor separation. As a result, the phase diagram of the system recalls that of water up to moderate (i.e., a few tens MPa) pressures. Upon superimposing a suitable hard core on the double-Gaussian potential, a further transition to a more compact solid phase is induced at high pressure, which might be regarded as the analog of the ice I to ice III transition in water.
Isotropic pair potentials that are bounded at the origin have been proposed from time to time as models of the effective interaction between macromolecules of interest in the chemical physics of soft matter. We present a thorough study of the phase b
ehavior of point particles interacting through a potential which combines a bounded short-range repulsion with a much weaker attraction at moderate distances, both of Gaussian shape. Notwithstanding the fact that the attraction acts as a small perturbation of the Gaussian-core model potential, the phase diagram of the double-Gaussian model (DGM) is far richer, showing two fluid phases and four distinct solid phases in the case that we have studied. Using free-energy calculations, the various regions of confluence of three distinct phases in the DGM system have all been characterized in detail. Moreover, two distinct lines of reentrant melting are found, and for each of them a rationale is provided in terms of the elastic properties of the solid phases.
In standard nucleation theory, the nucleation process is characterized by computing $DeltaOmega(V)$, the reversible work required to form a cluster of volume $V$ of the stable phase inside the metastable mother phase. However, other quantities beside
s the volume could play a role in the free energy of cluster formation, and this will in turn affect the nucleation barrier and the shape of the nucleus. Here we exploit our recently introduced mesoscopic theory of nucleation to compute the free energy cost of a nearly-spherical cluster of volume $V$ and a fluctuating surface area $A$, whereby the maximum of $DeltaOmega(V)$ is replaced by a saddle point in $DeltaOmega(V,A)$. Compared to the simpler theory based on volume only, the barrier height of $DeltaOmega(V,A)$ at the transition state is systematically larger by a few $k_BT$. More importantly, we show that, depending on the physical situation, the most probable shape of the nucleus may be highly non spherical, even when the surface tension and stiffness of the model are isotropic. Interestingly, these shape fluctuations do not influence or modify the standard Classical Nucleation Theory manner of extracting the interface tension from the logarithm of the nucleation rate near coexistence.
We present a Monte Carlo simulation study of the phase behavior of two-dimensional classical particles repelling each other through an isotropic Gaussian potential. As in the analogous three-dimensional case, a reentrant-melting transition occurs upo
n compression for not too high temperatures, along with a spectrum of water-like anomalies in the fluid phase. However, in two dimensions melting is a continuous two-stage transition, with an intermediate hexatic phase which becomes increasingly more definite as pressure grows. All available evidence supports the Kosterlitz-Thouless-Halperin-Nelson-Young scenario for this melting transition. We expect that such a phenomenology can be checked in confined monolayers of charge-stabilized colloids with a softened core.
