Abstract. We study the electrostatic Casimir effect and related phenomena in equilibrium statistical mechanics of classical (non-quantum) charged fluids. The prototype model consists of two identical dielectric slabs in empty space (the pure Casimir effect) or in the presence of an electrolyte between the slabs. In the latter case, it is generally believed that the long-ranged Casimir force due...

A previous analytical investigation of the generalized Born (GB) implicit solvation model is extended to solvents of nonzero ionic strength. The GB model with salt effects (GB-SE) is shown to resemble the Debye-Hückel-like screening model (DESMO), a polarizable continuum model (PCM) that we have recently developed for salty solutions. DESMO may be regarded either as a generalization of the cond...

We show that hydrophilic ions present in a confined, near-critical aqueous mixture can lead to an attraction between like charge surfaces with opposing preferential adsorption of the two species of the mixture, even though the corresponding Casimir potential in uncharged systems is repulsive. This prediction agrees with a recent experiment [Nellen et al., Soft Matter, 2011, 7, 5360]. We also sh...

The Debye–Hückel Limiting Law (DHLL) correctly predicts the thermodynamic behavior of dilute electrolyte solutions. Most articles and books explain this law using Peter Debye Erich Hückel’s original formalism linearizing Poisson–Boltzmann equation for a simple model. Brilliant in its own right, approach does not fully which microstates contribute range theory. Notably, establish Energy Multipli...

Two overall neutral surfaces with positively and negatively charged domains ("patches") have been shown in recent experiments to exhibit long-range attraction when immersed in an ionic solution. Motivated by the experiments, we calculate analytically the osmotic pressure between such surfaces within the Poisson-Boltzmann framework, using a variational principle for the surface-averaged free ene...

Simulations of the Lebowitz length, xiL (T, rho), are reported for the restricted primitive model hard-core (diameter a) 1:1 electrolyte for densities rho approximately < 4rho(c) and T(c) approximately < T approximately < 40T(c). Finite-size effects are elucidated for the charge fluctuations in various subdomains that serve to evaluate xiL. On extrapolation to the bulk limit for T approximately...

It has been argued that for a finite two-dimensional classical Coulomb system of characteristic size R, in its conducting phase, as R → ∞ the total free energy (times the inverse temperature β) admits an expansion of the form: βF = AR +BR+ 1 6 χ lnR, where χ is the Euler characteristic of the manifold where the system lives. The first two terms represent the bulk free energy and the surface fre...

Abstract. We study the electrostatic Casimir effect and related phenomena in equilibrium statistical mechanics of classical (non-quantum) charged fluids. The prototype model consists of two identical dielectric slabs in empty space (the pure Casimir effect) or in the presence of an electrolyte between the slabs. In the latter case, it is generally believed that the long-ranged Casimir force due...

In this chapter, we review our recent theoretical work on the formation of polyelectrolyte multilayers. The first layer is obtained by polyelectrolyte adsorption on a surface with an opposite charge. The adsorbed polyelectrolyte charge is sufficient to invert the charge of the surface. Each subsequent layer is bound to the previous one by the formation of a polyelectrolyte complex. Using a Deby...

Dense suspensions of small strongly interacting particles are complex systems that are rarely understood on the microscopic level. We investigate properties of dense suspensions and sediments of small spherical Al2O3 particles in a shear cell by means of a combined molecular-dynamics and stochastic rotation dynamics simulation. We study structuring effects and the dependence of the suspension's...