title: Isomorphous substitution in bimetallic oxide clusters.
abstract: The geometric and electronic structure of bimetallic oxide clusters is studied as a function of their composition with gas phase vibrational spectroscopy. Infrared multiple photon dissociation spectra of titanium-vanadium oxide cluster anions are measured in the 500 to 1200 wave number range and assigned on the basis of harmonic frequencies calculated using density functional theory. Singly substituted (V(2)O(5))(n-1)(VTiO(5))(-) (n=2-4) cluster anions are shown to form polyhedral caged structures similar to those predicted for their isoelectronic counterparts, the neutral (V(2)O(5))(n) clusters. Upon systematic exchange of V by Ti atoms in V(4-n)Ti(n)O(-)(10) (n=1-4), the structure does not change. The stress induced by the isomorphous substitution results in an increased number of unpaired electrons (n-1) for the Ti-rich systems, leading to a quartet ground state for Ti(4)O(-)(10).
authors.affiliation: Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, D-14195 Berlin, Germany. janssens@physik.fu-berlin.de
authors.forename: E
authors.initials: E
authors.lastname: Janssens
authors.forename: G
authors.initials: G
authors.lastname: Santambrogio
authors.forename: M
authors.initials: M
authors.lastname: Brümmer
authors.forename: L
authors.initials: L
authors.lastname: Wöste
authors.forename: P
authors.initials: P
authors.lastname: Lievens
authors.forename: J
authors.initials: J
authors.lastname: Sauer
authors.forename: G
authors.initials: G
authors.lastname: Meijer
authors.forename: K R
authors.initials: KR
authors.lastname: Asmis