Condensation and evaporation transitions in deep capillary grooves

We study the order of capillary condensation and evaporation transitions of a simple fluid adsorbed in a deep capillary groove using a fundamental measure density functional theory (DFT). The walls of the capillary interact with the fluid particles via long-ranged, dispersion, forces while the fluid-fluid interaction is modelled as a truncated Lennard-Jones-like potential. We find that below the wetting temperature $T_w$ condensation is first-order and evaporation is continuous with the metastability of the condensation being well described by the complementary Kelvin equation. In contrast above $T_w$ both phase transitions are continuous and their critical singularities are determined. In addition we show that for the evaporation transition above $T_w$ there is an elegant mapping, or covariance, with the complete wetting transition occurring at a planar wall. Our numerical DFT studies are complemented by analytical slab model calculations which explain how the asymmetry between condensation and evaporation arises out of the combination of long-ranged forces and substrate geometry

Crystallisation of soft matter under confinement at interfaces and in wedges

The surface freezing and surface melting transitions exhibited by a model two-dimensional soft matter system is studied. The behaviour when confined within a wedge is also considered. The system consists of particles interacting via a soft purely repulsive pair potential. Density functional theory (DFT) is used to calculate density profiles and thermodynamic quantities. The external potential due to the confining walls is modelled via a hard-wall with an additional repulsive Yukawa potential. The surface phase behaviour depends on the range and strength of this repulsion: When the repulsion strength is weak, the wall promotes freezing at the surface of the wall. The thickness of this frozen layer grows logarithmically as the bulk liquid-solid phase coexistence is approached. Our mean-field DFT predicts that this crystalline layer at the wall must be nucleated (i.e. there is a free energy barrier) and its formation is necessarily a first-order transition, referred to as `prefreezing', by analogy with the prewetting transition. However, in contrast to the latter, prefreezing cannot terminate in a critical point, since the phase transition involves a change in symmetry. If the wall-fluid interaction is sufficiently long ranged and the repulsion is strong enough, surface melting can instead occur. Then the interface between the wall and the bulk crystalline solid becomes wet by the liquid phase as the chemical potential is decreased towards the value at liquid-solid coexistence. It is observed that the finite thickness fluid film at the wall has a broken translational symmetry due to its proximity to the bulk crystal and so the nucleation of the wetting film can be either first-order or continuous. Our mean-field theory predicts that for certain wall potentials there is a premelting critical point analogous to the surface critical point for the prewetting transition. In a wedge...Comment: 11 pages, 12 figure

Low-temperature and high-temperature approximations for penetrable-sphere fluids. Comparison with Monte Carlo simulations and integral equation theories

The two-body interaction in dilute solutions of polymer chains in good solvents can be modeled by means of effective bounded potentials, the simplest of which being that of penetrable spheres (PSs). In this paper we construct two simple analytical theories for the structural properties of PS fluids: a low-temperature (LT) approximation, that can be seen as an extension to PSs of the well-known solution of the Percus-Yevick (PY) equation for hard spheres, and a high-temperature (HT) approximation based on the exact asymptotic behavior in the limit of infinite temperature. Monte Carlo simulations for a wide range of temperatures and densities are performed to assess the validity of both theories. It is found that, despite their simplicity, the HT and LT approximations exhibit a fair agreement with the simulation data within their respective domains of applicability, so that they complement each other. A comparison with numerical solutions of the PY and the hypernetted-chain approximations is also carried out, the latter showing a very good performance, except inside the core at low temperatures.Comment: 14 pages, 8 figures; v2: some figures redone; small change