title: Oxygen adsorption on gold nanofacets and model clusters.
abstract: We have studied oxygen interaction with Au crystals (field emitter tips) using time-resolved (atom-probe) field desorption mass spectrometry. The results demonstrate no adsorption to take place on clean Au facets under chosen conditions of pressures (p < 10(-4) m/bar) and temperatures (T = 300-350 K). Steady electric fields of 6 V/nm do not allow dissociating the oxygen molecule. The measured O2+ intensities rather reflect ionization of O2 molecules at critical distances above the Au tip surface. Certain amounts of Au-O2 complex ions can be found at the onset of Au field evaporation. Calculations by density functional theory (DFT) show weak oxygen end-on interaction with Au10 clusters (Delta E = 0.023 eV) and comparatively stronger interaction with Au1/Au(100) model surfaces (Delta E = 0.25 eV). No binding is found on {210} facets. Including (positive) electric fields in the DFT calculations leads to an increase of the activation energy for oxygen dissociation thus providing an explanation for the absence of atomic oxygen ions from the field desorption mass spectra.
authors.affiliation: Chemical Physics of Materials, Université Libre de Bruxelles, Campus Plaine, CP 243, 1050 Brussels, Belgium.
authors.forename: T
authors.initials: T
authors.lastname: Visart de Bocarmé
authors.forename: T-D
authors.initials: TD
authors.lastname: Chau
authors.forename: F
authors.initials: F
authors.lastname: Tielens
authors.forename: J
authors.initials: J
authors.lastname: Andrés
authors.forename: P
authors.initials: P
authors.lastname: Gaspard
authors.forename: R L C
authors.initials: RL
authors.lastname: Wang
authors.forename: H J
authors.initials: HJ
authors.lastname: Kreuzer
authors.forename: N
authors.initials: N
authors.lastname: Kruse