Solvation of Nanoions in Aqueous Solutions

In recent years it has been increasingly recognized that different classes of large ions with multiple valency have effects conceptually similar to weakly solvated ions in the Hofmeister series, also labeled by the term chaotropic. The term “super- chaotropic effect” has been coined, because these effects are much stronger pronounced for nanometer-sized ions, whose adsorption properties often resemble typical surfac- tants. Despite this growing interest in these nanometer-sized ions, a simple conceptual extension of the Hofmeister series towards nanoions has not been achieved, because an extrapolation of the one-dimensional surface charge density scale does not lead to the superchaotropic regime. In this work, we discuss a generic model that is broadly appli- cable to ions of nearly shperical shape and thus includes polyoxometallates and boron clusters. We present a qualitative classification scheme, in which the ion size appears as a second dimension. Ions of different size but same charge density differ in their bulk solvation free energy. As the ions grow bigger at constant surface charge density, they become more stable in solution, but the adsorption behavior is still governed by the surface charge density. A detailed molecular dynamics simulation study of large ions that is based on a shifted Lennard-Jones potential is presented that supports the presented classification scheme.