Joint density-functional theory:: Ab initio study of Cr2O3 surface chemistry in solution

After introducing a new form of density-functional theory for the ab initio description of electronic systems in contact with a molecular liquid environment, we present the first detailed study of the impact of a solvent on the surface chemistry of Cr2O3, the passivating layer of stainless steel alloys. In comparison to a vacuum, we predict that the presence of water has little impact on the adsorption of chloride ions to the oxygenterminated surface but has a dramatic effect on the binding of hydrogen to that surface. These results indicate that the dielectric screening properties of water are important to the passivating effects of the oxygen-terminated surface.