Surface Propensities of the Self-Ions of Water.

Abstract

The surface charge of water, which is important in a wide range of chemical, biological, material, and environmental contexts, has been a subject of lengthy and heated debate. Recently, it has been shown that the highly efficient LEWIS force field, in which semiclassical, independently mobile valence electron pairs capture the amphiproticity, polarizability and H-bonding of water, provides an excellent description of the solvation and dynamics of hydroxide and hydronium in bulk water. Here we turn our attention to slabs, cylinders, and droplets. In extended simulations with 1000 molecules, we find that hydroxide consistently prefers the surface, hydronium consistently avoids the surface, and the two together form an electrical double layer until neutralization occurs. The behavior of hydroxide can largely be accounted for by the observation that hydroxide moving to the surface loses fewer hydrogen bonds than are gained by the water molecule that it displaces from the surface. At the same time, since the orientation of the hydroxide increases the ratio of dangling hydrogens to dangling lone pairs, the proton activity of the exposed surface may be increased, rather than decreased. Hydroxide also moves more rapidly in the surface than in the bulk, likely because the proton donating propensity of neighboring water molecules is focused on the one hydrogen that is not dangling from the surface.