Electrochemical processes occurring in aqueous solutions are critically dependent upon the interaction between the metal electrode and the solvent. In this work, density functional theory is used to calculate the potentials for which molecular water and its activation products (adsorbed hydrogen and hydroxide) are stable when in contact with an immersed Ni(111) electrode. The adsorption geometries of water and its dissociation products are also determined as functions of potential. At zero kelvin, water activates to form a surface hydroxide overlayer at potentials anodic of - 0.5 V vs a normal hydrogen electrode (NHE). The cathodic activation of water to form a surface hydride occurs at potentials negative of - 0.3 V NHE. There is a potential range at which both H and OH form on the surface, in agreement with inferences made from the experimental literature. The surface hydroxide/oxide phase transition occurs at 0.2 V NHE. The increased binding of oxygen to the surface at progressively anodic potentials correlates with weakening nickel-nickel interactions and the lifting of a metal atom above the surface plane. Thermodynamic extrapolations are made to ambient (300K) and elevated (600K) temperatures and Pourbaix diagrams calculated for the inert and activated surface phases of water on Ni (111) and compared with experiment. (c) 2006 The Electrochemical Society.