Electrostatic contribution to the ion solvation energy: cavity effects

Ion solvation process has been analysed for the spherically symmetrical system where an ion is located inside a cavity surrounded by an isotropic nonlocal dielectric medium. It has been proven that for any dielectric properties of the medium, the electric field outside the cavity as well as the ion solvation energy depend only on the total ion charge but not of the particular distribution of the ion charge density inside the cavity. These characteristics remain unchanged if the charge is displaced from the external boundary of the cavity into it. Analytical formulas for them have been derived for a particular model of the nonlocal dielectric function. Comparison of results for the solvation energy on the basis of this new theory and of the conventional approach (disregarding the existence of the cavity) shows a significant difference between their predictions if the ion charge is displaced inside the ion cavity.