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 (V2O5)(n-1)(VTiO5)(-) (n=2-4) cluster anions are shown to form polyhedral caged structures similar to those predicted for their isoelectronic counterparts, the neutral (V2O5)(n) clusters. Upon systematic exchange of V by Ti atoms in V4-nTinO10- (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 Ti4O10-.
Isomorphous substitution in bimetallic oxide clusters / Janssens, E., Santambrogio, G., Brummer, M., Woste, L., Lievens, P., Sauer, J., Meijer, G., Asmis, K.r.. - In: PHYSICAL REVIEW LETTERS. - ISSN 0031-9007. - 96:23(2006), pp. 233401-1-4. [10.1103/PhysRevLett.96.233401]
Isomorphous substitution in bimetallic oxide clusters
SANTAMBROGIO, GABRIELE;
2006
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 (V2O5)(n-1)(VTiO5)(-) (n=2-4) cluster anions are shown to form polyhedral caged structures similar to those predicted for their isoelectronic counterparts, the neutral (V2O5)(n) clusters. Upon systematic exchange of V by Ti atoms in V4-nTinO10- (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 Ti4O10-.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
