We have performed reactive trajectory calculations of proton discharge on charged platinum surfaces as a function of temperature and charge. A recently developed 9-state empirical valence bond model has been employed. The temperature dependence follows an Arrhenius law with activation energies in the range of 0.1 eV. The activation energy for the discharge reaction decreases significantly with increasing driving force as modeled by an increasingly negative surface charge on the electrode. The analysis shows that the average orientation of molecules in the adsorbed water layer reacts to the approaching proton. Within increasing temperature, configurations become more prevalent which facilitate fast proton transfer by Grotthuss style proton hops from the second to the first layer. This effect becomes more pronounced near more negatively charged surfaces and leads to the computed reduction of the activation energy. (C) 2013 Elsevier Ltd. All rights reserved.