Screening of Spherical Colloids beyond Mean Field -- A Local Density Functional Approach

Abstract

We study the counterion distribution around a spherical macroion and its osmotic pressure in the framework of the recently developed Debye-H"uckel-Hole-Cavity (DHHC) theory. This is a local density functional approach which incorporates correlations into Poisson-Boltzmann theory by adding a free energy correction based on the One Component Plasma. We compare the predictions for ion distribution and osmotic pressure obtained by the full theory and by its zero temperature limit with Monte Carlo simulations. They agree excellently for weakly developed correlations and give the correct trend for stronger ones. In all investigated cases the DHHC theory and its computationally simpler zero temperature limit yield better results than the Poisson-Boltzmann theory.