Stern Layer Structure and Energetics at Mica–Water Interfaces

Abstract

The screening of surface charge by dissolved ions at solid−liquid interfacesin the region of interfacial fluid known as the electrical double layer (EDL)plays a recurrent role in surface science, from ion adsorption to colloidal mechanics to the transport properties of nanoporous media. A persistent unknown in theories of EDL-related phenomena is the structure of the Stern layer, the near-surface portion of the EDL where water molecules and adsorbed ions form specific short-range interactions with surface atoms. Here, we describe a set of synchrotron X-ray reflectivity (XRR) experiments and molecular dynamics (MD) simulations carried out under identical conditions for a range of 0.1 M alkali chloride (Li-, Na-, K-, Rb-, or CsCl) solutions on the basal surface of muscovite mica, a mineral isostructural to phyllosilicate clay minerals and one of the most widely studied reference surfaces in interfacial science. Our XRR and MD simulation results provide a remarkably consistent view of the structure and energetics of the Stern layer, with some discrepancy on the fraction of the minor outer-sphere component of Rb and on the adsorption energetics of Li. The results of both techniques, along with surface complexation model calculations, provide insight into the sensitivity of water structure and ion adsorption to surface topography and the type of adsorbed counterion