Abstract
Ion specificity and related Hofmeister effects, which are ubiquitous in aqueous systems, can have spectacular consequences in hydrated clays, where ion-specific nanoscale surface forces can determine large-scale cohesive swelling and shrinkage behaviors of soil and sediments. We have used a semiatomistic computational approach and examined sodium, calcium, and aluminum counterions confined with water between charged surfaces representative of clay materials to show that ion−water structuring in nanoscale confinement is at the origin of surface forces between clay particles which are intrinsically ionspecific. When charged surfaces strongly confine ions and water, the amplitude and oscillations of the net pressure naturally emerge from the interplay of electrostatics and steric effects, which cannot be captured by existing theories. Increasing confinement and surface charge densities promote ion−water structures that increasingly deviate from the ions' bulk hydration shells, being strongly anisotropic, persistent, and self-organizing into optimized, nearly solid-like assemblies where hardly any free water is left. Under these conditions, strongly attractive interactions can prevail between charged surfaces because of the dramatically reduced dielectric screening of water and the highly organized water−ion structures. By unravelling the ion-specific nature of these nanoscale interactions, we provide evidence that ion-specific solvation structures determined by confinement are at the origin of ion specificity in clays and potentially a broader range of confined aqueous systems.