XPS of Oxygen Atoms on Ag(111) and Ag(110) Surfaces: Accurate Study with SAC/SAC-CI Combined with Dipped Adcluster Model

O1s core-electron binding energies (CEBE) of the atomic oxygens on different Ag surfaces were investigated by the symmetry adapted cluster-configuration interaction (SAC-CI) method combined with the dipped adcluster model, in which the electron exchange between bulk metal and adsorbate is taken into account properly. Electrophilic and nucleophilic oxygens (O-elec and O-nuc) that might be important for olefin epoxidation in a low-oxygen coverage condition were focused here. We consider the O1s CEBE as a key property to distinguish the surface oxygen states, and series of calculation was carried out by the Hartree-Fock, Density functional theory, and SAC/SAC-CI methods. The experimental information and our SAC/SAC-CI results indicate that O-elec is the atomic oxygen adsorbed on the fcc site of Ag(111) and that O-nuc is the one on the reconstructed added-row site of Ag(110) and that one- and two-electron transfers occur, respectively, to the O-elec and O-nuc adclusters from the silver surface. (c) 2013 Wiley Periodicals, Inc.