Fluid structure in the immediate vicinity of an equilibrium three-phase contact line and assessment of disjoining pressure models using density functional theory

We examine the nanoscale behavior of an equilibrium three-phase contact line in the presence of long-ranged intermolecular forces by employing a statistical mechanics of fluids approach, namely density functional theory (DFT) together with fundamental measure theory (FMT). This enables us to evaluate the predictive quality of effective Hamiltonian models in the vicinity of the contact line. In particular, we compare the results for mean field effective Hamiltonians with disjoining pressures defined through (I) the adsorption isotherm for a planar liquid film, and (II) the normal force balance at the contact line. We find that the height profile obtained using (I) shows good agreement with the adsorption film thickness of the DFT-FMT equilibrium density profile in terms of maximal curvature and the behavior at large film heights. In contrast, we observe that while the height profile obtained by using (II) satisfies basic sum rules, it shows little agreement with the adsorption film thickness of the DFT results. The results are verified for contact angles of 20, 40 and 60 degrees

Exact Casimir interaction between eccentric cylinders

The Casimir force is the ultimate background in ongoing searches of extra-gravitational forces in the micrometer range. Eccentric cylinders offer favorable experimental conditions for such measurements as spurious gravitational and electrostatic effects can be minimized. Here we report on the evaluation of the exact Casimir interaction between perfectly conducting eccentric cylinders using a mode summation technique, and study different limiting cases of relevance for Casimir force measurements, with potential implications for the understanding of mechanical properties of nanotubes.Comment: 5 pages, 4 figure

Nonlinear screening of charged macromolecules

We present several aspects of the screening of charged macromolecules in an electrolyte. After a review of the basic mean field approach, based on the linear Debye-Huckel theory, we consider the case of highly charged macromolecules, where the linear approximation breaks down and the system is described by full nonlinear Poisson-Boltzmann equation. Some analytical results for this nonlinear equation give some interesting insight on physical phenomena like the charge renormalization and the Manning counterion condensation

Dynamics of liquid nanofilms

The van der Waals forces across a very thin liquid layer (nanofilm) in contact with a plane solid wall make the liquid nonhomogeneous. The dynamics of such flat liquid nanofilms is studied in isothermal case. The Navier-Stokes equations are unable to describe fluid motions in very thin films. The notion of surface free energy of a sharp interface separating gas and liquid layer is disqualified. The concept of disjoining pressure replaces the model of surface energy. In the nanofilm a supplementary free energy must be considered as a functional of the density. The equation of fluid motions along the nanofilm is obtained through the Hamilton variational principle by adding, to the conservative forces, the forces of viscosity in lubrication approximation. The evolution equation of the film thickness is deduced and takes into account the variation of the disjoining pressure along the layer.Comment: 13 pages. International Journal of Engineering Science / International Journal of Engineering Sciences 46 (2008) to appea

Ground state of two unlike charged colloids: An analogy with ionic bonding

In this letter, we study the ground state of two spherical macroions of identical radius, but asymmetric bare charge ((Q_{A}>Q_{B})). Electroneutrality of the system is insured by the presence of the surrounding divalent counterions. Using Molecular Dynamics simulations within the framework of the primitive model, we show that the ground state of such a system consists of an overcharged and an undercharged colloid. For a given macroion separation the stability of these ionized-like states is a function of the difference ((\sqrt{N_{A}}-\sqrt{N_{B}})) of neutralizing counterions (N_{A}) and (N_{B}). Furthermore the degree of ionization, or equivalently, the degree of overcharging, is also governed by the distance separation of the macroions. The natural analogy with ionic bonding is briefly discussed.Comment: published versio

Proximity Effects in Radiative Transfer

Though the dependence of near-field radiative transfer on the gap between two planar objects is well understood, that between curved objects is still unclear. We show, based on the analysis of the surface polariton mediated radiative transfer between two spheres of equal radii $R$ and minimum gap $d$, that the near--field radiative transfer scales as $R/d$ as $d/R \rightarrow 0$ and as $\ln(R/d)$ for larger values of $d/R$ up to the far--field limit. We propose a modified form of the proximity approximation to predict near--field radiative transfer between curved objects from simulations of radiative transfer between planar surfaces.Comment: 5 journal pages, 4 figure

Studies on electrostatic interactions of colloidal particles under two-dimensional confinement

We study the effective electrostatic interactions between a pair of charged colloidal particles without salt ions while the system is confined in two dimensions. In particular we use a simplified model to elucidate the effects of rotational fluctuations in counterion distribution. The results exhibit effective colloidal attractions under appropriate conditions. Meanwhile, long-range repulsions persist over most of our studied cases. The repulsive forces arise from the fact that in two dimensions the charged colloids cannot be perfectly screened by counterions, as the residual quadrupole moments contribute to the repulsions at longer range. And by applying multiple expansions we find that the attractive forces observed at short range are mainly contributed from electrostatic interactions among higher-order electric moments. We argue that the scenario for attractive interactions discussed in this work is applicable to systems of charged nanoparticles or colloidal solutions with macroions.Comment: 23 pages, 11 figures, 1 tabl

Effective interactions in the colloidal suspensions from HNC theory

The HNC Ornstein-Zernike integral equations are used to determine the properties of simple models of colloidal solutions where the colloids and ions are immersed in a solvent considered as a dielectric continuum and have a size ratio equal to 80 and a charge ratio varying between 1 and 4000. At an infinite dilution of colloids, the effective interactions between colloids and ions are determined for ionic concentrations ranging from 0.001 to 0.1 mol/l and compared to those derived from the Poisson-Boltzmann theory. At finite concentrations, we discuss on the basis of the HNC results the possibility of an unambiguous definition of the effective interactions between the colloidal molecules.Comment: 26 pages, 15 figure

Screening of charged spheroidal colloidal particles

We study the effective screened electrostatic potential created by a spheroidal colloidal particle immersed in an electrolyte, within the mean field approximation, using Poisson--Botzmann equation in its linear and nonlinear forms, and also beyond the mean field by means of Monte Carlo computer simulation. The anisotropic shape of the particle has a strong effect on the screened potential, even at large distances (compared to the Debye length) from it. To quantify this anisotropy effect, we focus our study on the dependence of the potential on the position of the observation point with respect with the orientation of the spheroidal particle. For several different boundary conditions (constant potential, or constant surface charge) we find that, at large distance, the potential is higher in the direction of the large axis of the spheroidal particle