title: Electric field induced electron transfer at the adsorbate-surface interface. Effect of the type of metal surface.
abstract: The ab initio two-state model for electron transfer induced by an external electric field has been applied to the chloride oxidation on Cu, Rh, Pd, Ag, Pt and Au (001) surface models. The two electronic states involved in the model represent physical situations where the electron transferred from the chloride anion to the metal surface lies either on the halide or on the metal substrate. The model assumes that electron transfer takes place when these two states become degenerate and this is achieved by applying an external electric field. Two different situations representing either ultrahigh vacuum or electrochemical conditions have been considered. For the former the present study shows that electric field necessary to achieve degeneracy of the two electronic states is directly related to the metal surface work function whereas for the latter, it is found to be rather insensitive to the metal surface.
authors.affiliation: Departament de Química Física & CeRQT, Universitat de Barcelona & Parc Científic de Barcelona, C/Martí i Franquès 1, E-08028, Barcelona, Spain.
authors.forename: Annapaola
authors.initials: A
authors.lastname: Migani
authors.forename: Carmen
authors.initials: C
authors.lastname: Sousa
authors.forename: Fausto
authors.initials: F
authors.lastname: Sanz
authors.forename: Francesc
authors.initials: F
authors.lastname: Illas
mesh_terms: D000465:Algorithms; D002712:Chlorides / Q000737:chemistry; D004563:Electrochemistry; D004583:Electrons; D019216:Metals, Heavy / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D013499:Surface Properties
chemical_list: D002712:Chlorides; D019216:Metals, Heavy