The infrared spectra of the binary vanadium oxide cluster anions V(4)O(9)(-) and V(4)O(10)(-) and of the related methoxo clusters V(4)O(9)(OCH(3))(-) and V(4)O(8)(OCH(3))(2)(-) are recorded in the gas phase by photodissociation of the mass-selected ions using an infrared loser. For the oxide clusters V(4)O(9)(-) and V(4)O(10)(-), the bonds of the terminal vanadyl oxygen atoms, nu(V-O(t)), and of the bridging oxygen atoms, nu(V-O(b)-V), are identified clearly. The clusters in which one or two of the oxo groups are replaced by methoxo ligands show additional absorptions which are assigned to the C-O stretch, nu(C-O). Density functional calculations are used as a complement for the experimental studies and the interpretation of the infrared spectra. The results depend in on unusual way on the functional employed (BLYP versus B3LYP), which is due to the presence of both V-O(CH(3)) single and V=O double bonds as terminal bonds and to the strong multireference character of the latter.

Gas-phase infrared photodissociation spectroscopy of tetravanadiumoxo and oxo-methoxo cluster anions / Feyel, S; Schwarz, H; Schroder, D; Daniel, C; Hartl, H; Dobler, J; Sauer, J; Santambrogio, Gabriele; Woste, L; Asmis, Kr. - In: CHEMPHYSCHEM. - ISSN 1439-4235. - 8:11(2007), pp. 1640-1647. [10.1002/cphc.200700255]

Gas-phase infrared photodissociation spectroscopy of tetravanadiumoxo and oxo-methoxo cluster anions

SANTAMBROGIO, GABRIELE;
2007

Abstract

The infrared spectra of the binary vanadium oxide cluster anions V(4)O(9)(-) and V(4)O(10)(-) and of the related methoxo clusters V(4)O(9)(OCH(3))(-) and V(4)O(8)(OCH(3))(2)(-) are recorded in the gas phase by photodissociation of the mass-selected ions using an infrared loser. For the oxide clusters V(4)O(9)(-) and V(4)O(10)(-), the bonds of the terminal vanadyl oxygen atoms, nu(V-O(t)), and of the bridging oxygen atoms, nu(V-O(b)-V), are identified clearly. The clusters in which one or two of the oxo groups are replaced by methoxo ligands show additional absorptions which are assigned to the C-O stretch, nu(C-O). Density functional calculations are used as a complement for the experimental studies and the interpretation of the infrared spectra. The results depend in on unusual way on the functional employed (BLYP versus B3LYP), which is due to the presence of both V-O(CH(3)) single and V=O double bonds as terminal bonds and to the strong multireference character of the latter.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11696/29444
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