title: Copper doping of small gold cluster cations: influence on geometric and electronic structure.
abstract: The effect of Cu doping on the properties of small gold cluster cations is investigated in a joint experimental and theoretical study. Temperature-dependent Ar tagging of the clusters serves as a structural probe and indicates no significant alteration of the geometry of Au(n) (+) (n = 1-16) upon Cu doping. Experimental cluster-argon bond dissociation energies are derived as a function of cluster size from equilibrium mass spectra and are in the 0.10-0.25 eV range. Near-UV and visible light photodissociation spectroscopy is employed in conjunction with time-dependent density functional theory calculations to study the electronic absorption spectra of Au(4-m)Cu(m) (+) (m = 0, 1, 2) and their Ar complexes in the 2.00-3.30 eV range and to assign their fragmentation pathways. The tetramers Au(4) (+), Au(4) (+)[middle dot]Ar, Au(3)Cu(+), and Au(3)Cu(+)[middle dot]Ar exhibit distinct optical absorption features revealing a pronounced shift of electronic excitations to larger photon energies upon substitution of Au by Cu atoms. The calculated electronic excitation spectra and an analysis of the character of the optical transitions provide detailed insight into the composition-dependent evolution of the electronic structure of the clusters.
authors.affiliation: Laboratory of Solid State Physics and Magnetism, Katholieke Universiteit Leuven, Celestijnenlaan 200D, B-3001 Leuven, Belgium.
authors.forename: Sandra M
authors.initials: SM
authors.lastname: Lang
authors.forename: Pieterjan
authors.initials: P
authors.lastname: Claes
authors.forename: Ngo Tuan
authors.initials: NT
authors.lastname: Cuong
authors.forename: Minh Tho
authors.initials: MT
authors.lastname: Nguyen
authors.forename: Peter
authors.initials: P
authors.lastname: Lievens
authors.forename: Ewald
authors.initials: E
authors.lastname: Janssens