The structure and energetics of two types of oxygen-terminated diamond surfaces, the keto and ether configurations, were investigated by density functional theory. To explore OH generation, we studied the approach of a hydroxyl radical to these surfaces. The OH radical strongly interacted with the ether-type surface, whereas the radical was repelled in the keto configuration. The kinetics of OH generation in alkaline solutions (OH−↔OH+e−) on oxygen-terminated diamond electrodes was investigated in light of the theory of catalyzed electron transfer. Our results suggested that the electron transfer occurs in the outer-sphere mode with an activation energy of 0.5 eV.Fil: Quaino, Paola Monica. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Schmickler, Wolfgang. Universitat Ulm; Alemania. Institute of Theoretical Chemistry; Alemania