Surface tension of electrolytes: Hydrophilic and hydrophobic ions near an interface

We calculate the ion distributions around an interface in fluid mixtures of highly polar and less polar fluids (water and oil) for two and three ion species. We take into account the solvation and image interactions between ions and solvent. We show that hydrophilic and hydrophobic ions tend to undergo a microphase separation at an interface, giving rise to an enlarged electric double layer. We also derive a general expression for the surface tension of electrolyte systems, which contains a negative electrostatic contribution proportional to the square root of the bulk salt density. The amplitude of this square-root term is small for hydrophilic ion pairs, but is much increased for hydrophilic and hydrophobic ion pairs. For three ion species including hydrophilic and hydrophobic ions, we calculate the ion distributions to explain those obtained by x-ray reflectivity measurements.Comment: 8 figure

Gas Enrichment at Liquid-Wall Interfaces

Molecular dynamics simulations of Lennard-Jones systems are performed to study the effects of dissolved gas on liquid-wall and liquid-gas interfaces. Gas enrichment at walls is observed which for hydrophobic walls can exceed more than two orders of magnitude when compared to the gas density in the bulk liquid. As a consequence, the liquid structure close to the wall is considerably modified, leading to an enhanced wall slip. At liquid-gas interfaces gas enrichment is found which reduces the surface tension.Comment: main changes compared to version 1: flow simulations are included as well as different types of gase

Metastable liquid-liquid coexistence and density anomalies in a core-softened fluid

Linearly-sloped or `ramp' potentials belong to a class of core-softened models which possess a liquid-liquid critical point (LLCP) in addition to the usual liquid-gas critical point. Furthermore they exhibit thermodynamic anomalies in the density and compressibility, the nature of which may be akin to those occurring in water. Previous simulation studies of ramp potentials have focused on just one functional form, for which the LLCP is thermodynamically stable. In this work we construct a series of ramp potentials, which interpolate between this previously studied form and a ramp-based approximation to the Lennard-Jones (LJ) potential. By means of Monte Carlo simulation, we locate the LLCP, the first order high density liquid (HDL)-low density liquid (LDL) coexistence line, and the line of density maxima for a selection of potentials in the series. We observe that as the LJ limit is approached, the LLCP becomes metastable with respect to freezing into a hexagonal close packed crystalline solid. The qualitative nature of the phase behaviour in this regime shows a remarkable resemblance to that seen in simulation studies of accurate water models. Specifically, the density of the liquid phase exceeds that of the solid; the gradient of the metastable LDL-HDL line is negative in the pressure (p)-temperature (T) plane; while the line of density maxima in the p-T plane has a shape similar to that seen in water and extends well into the {\em stable} liquid region of the phase diagram. As such, our results lend weight to the `second critical point' hypothesis as an explanation for the anomalous behaviour of water.Comment: 7 pages, 8 figure

Interfacial tension of the isotropic--nematic interface in suspensions of soft spherocylinders

The isotropic to nematic transition in a system of soft spherocylinders is studied by means of grand canonical Monte Carlo simulations. The probability distribution of the particle density is used to determine the coexistence density of the isotropic and the nematic phases. The distributions are also used to compute the interfacial tension of the isotropic--nematic interface, including an analysis of finite size effects. Our results confirm that the Onsager limit is not recovered until for very large elongation, exceeding at least L/D=40, with L the spherocylinder length and D the diameter. For smaller elongation, we find that the interfacial tension increases with increasing L/D, in agreement with theoretical predictions.Comment: 8 pages, 7 figures, and also 1 tabl

Lattice Boltzmann Model for Axisymmetric Multiphase Flows

In this paper, a lattice Boltzmann (LB) model is presented for axisymmetric multiphase flows. Source terms are added to a two-dimensional standard lattice Boltzmann equation (LBE) for multiphase flows such that the emergent dynamics can be transformed into the axisymmetric cylindrical coordinate system. The source terms are temporally and spatially dependent and represent the axisymmetric contribution of the order parameter of fluid phases and inertial, viscous and surface tension forces. A model which is effectively explicit and second order is obtained. This is achieved by taking into account the discrete lattice effects in the Chapman-Enskog multiscale analysis, so that the macroscopic axisymmetric mass and momentum equations for multiphase flows are recovered self-consistently. The model is extended to incorporate reduced compressibility effects. Axisymmetric equilibrium drop formation and oscillations, breakup and formation of satellite droplets from viscous liquid cylindrical jets through Rayleigh capillary instability and drop collisions are presented. Comparisons of the computed results with available data show satisfactory agreement.Comment: 17 pages, 11 figures, to be published in Physical Review

Liquid-vapor interface of a polydisperse fluid

We report a Grand Canonical Monte Carlo simulation study of the liquid-vapor interface of a model fluid exhibiting polydispersity in terms of the particle size $\sigma$. The bulk density distribution, $\rho^0(\sigma)$, of the system is controlled by the imposed chemical potential distribution $\mu(\sigma)$. We choose the latter such that $\rho^0(\sigma)$ assumes a Schulz form with associated degree of polydispersity $\approx 14$. By introducing a smooth attractive wall, a planar liquid-vapor interface is formed for bulk state points within the region of liquid-vapor coexistence. Owing to fractionation, the pure liquid phase is enriched in large particles, with respect to the coexisting vapor. We investigate how the spatial non-uniformity of the density near the liquid-vapor interface affects the evolution of the local distribution of particle sizes between the limiting pure phase forms. We find (as previously predicted by density functional theory, Bellier-Castella {\em et al}, Phys. Rev. {\bf E65}, 021503 (2002)) a segregation of smaller particles to the interface. The magnitude of this effect is quantified for various $\sigma$ via measurements of the relative adsorption. Additionally, we consider the utility of various estimators for the interfacial width and highlight the difficulties of isolating the intrinsic contribution of polydispersity to this width.Comment: 9 pages, 10 Fig

Fluid-fluid demixing transitions in colloid--polyelectrolyte star mixtures

We derive effective interaction potentials between hard, spherical colloidal particles and star-branched polyelectrolytes of various functionalities and smaller size than the colloids. The effective interactions are based on a Derjaguin-like approximation, which is based on previously derived potentials acting between polyelectrolyte stars and planar walls. On the basis of these interactions we subsequently calculate the demixing binodals of the binary colloid--polyelectrolyte star mixture, employing standard tools from liquid-state theory. We find that the mixture is indeed unstable at moderately high overall concentrations. The system becomes more unstable with respect to demixing as the star functionality and the size ratio grow.Comment: 24 pages, 9 figures, submitted to Journal of Physics: Condensed Matte

New results for virial coefficients of hard spheres in D dimensions

We present new results for the virial coefficients B_k with k <= 10 for hard spheres in dimensions D=2,...,8.Comment: 10 pages, 5 figures, to appear in conference proceedings of STATPHYS 2004 in Pramana - Journal of Physic

Derivation of a Non-Local Interfacial Hamiltonian for Short-Ranged Wetting II: General Diagrammatic Structure

In our first paper, we showed how a non-local effective Hamiltionian for short-ranged wetting may be derived from an underlying Landau-Ginzburg-Wilson model. Here, we combine the Green's function method with standard perturbation theory to determine the general diagrammatic form of the binding potential functional beyond the double-parabola approximation for the Landau-Ginzburg-Wilson bulk potential. The main influence of cubic and quartic interactions is simply to alter the coefficients of the double parabola-like zig-zag diagrams and also to introduce curvature and tube-interaction corrections (also represented diagrammatically), which are of minor importance. Non-locality generates effective long-ranged many-body interfacial interactions due to the reflection of tube-like fluctuations from the wall. Alternative wall boundary conditions (with a surface field and enhancement) and the diagrammatic description of tricritical wetting are also discussed.Comment: (14 pages, 2 figures) Submitted J. Phys. Condens. Matte

Laterally driven interfaces in the three-dimensional Ising lattice gas

We study the steady state of a phase-separated driven Ising lattice gas in three dimensions using computer simulations with Kawasaki dynamics. An external force field F(z) acts in the x direction parallel to the interface, creating a lateral order parameter current j^x(z) which varies with distance z from the interface. Above the roughening temperature, our data for `shear-like' linear variation of F(z) are in agreement with the picture wherein shear acts as effective confinement in this system, thus supressing the interfacial capillary-wave fluctuations. We find sharper magnetisation profiles and reduced interfacial width as compared to equilibrium. Pair correlations are more suppressed in the vorticity direction y than in the driving direction; the opposite holds for the structure factor. Lateral transport of capillary waves occurs for those forms of F(z) for which the current j^x(z) is an odd function of z, for example the shear-like drive, and a `step-like' driving field. For a V-shaped driving force no such motion occurs, but capillary waves are suppressed more strongly than for the shear-like drive. These findings are in agreement with our previous simulation studies in two dimensions. Near and below the (equilibrium) roughening temperature the effective-confinement picture ceases to work, but the lateral motion of the interface persists.Comment: 20 pages, 11 figures, submitted to Phys. Rev.