title: Double layer effects in a model of proton discharge on charged electrodes.
abstract: We report first results on double layer effects on proton discharge reactions from aqueous solutions to charged platinum electrodes. We have extended a recently developed combined proton transfer/proton discharge model on the basis of empirical valence bond theory to include specifically adsorbed sodium cations and chloride anions. For each of four studied systems 800-1000 trajectories of a discharging proton were integrated by molecular dynamics simulations until discharge occurred. The results show significant influences of ion presence on the average behavior of protons prior to the discharge event. Rationalization of the observed behavior cannot be based solely on the electrochemical potential (or surface charge) but needs to resort to the molecular details of the double layer structure.
authors.affiliation: Faculty of Chemistry, Duisburg-Essen University, D-45117 Essen, Germany.
authors.forename: Johannes
authors.initials: J
authors.lastname: Wiebe
authors.affiliation: Faculty of Chemistry and Center for Computational Sciences and Simulation (CCSS), Universität Duisburg-Essen, D-45117 Essen, Germany.
authors.forename: Eckhard
authors.initials: E
authors.lastname: Spohr
keywords: electrocatalysis; interfacial electrochemistry; proton discharge; reactive force field; trajectory calculations