A cavity formation energy formula for hard spheres in simple electrolyte solutions

Abstract

A formula for cavity formation energy of a hard sphere in restricted primitive electrolyte solutions is derived based on the integral equation theory. Specifically, the contact values of radial distribution functions between the hard sphere and the ionic species, determined analytically from the first-order mean spherical approximation theory, are used to evaluate the cavity formation energy. In the large solute-size limit, the scaling relation of the cavity formation energy further leads to an analytical expression for the surface tension of the electrolyte solution near a curved interface. Our theory is applied to hard spheres immersed in restricted primitive electrolyte solutions, where the good agreement of the cavity formation energy with the hyper-netted chain theory demonstrates the accuracy of our theory.