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Gas‐Phase Infrared Photodissociation Spectroscopy of Tetravanadiumoxo and Oxo–Methoxo Cluster Anions
Author(s) -
Feyel Sandra,
Schwarz Helmut,
Schröder Detlef,
Daniel Charles,
Hartl Hans,
Döbler Jens,
Sauer Joachim,
Santambrogio Gabriele,
Wöste Ludger,
Asmis Knut R.
Publication year - 2007
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200700255
Subject(s) - photodissociation , chemistry , infrared spectroscopy , infrared , cluster (spacecraft) , ion , vanadium oxide , crystallography , density functional theory , phase (matter) , photochemistry , vanadium , analytical chemistry (journal) , inorganic chemistry , computational chemistry , physics , organic chemistry , chromatography , computer science , optics , programming language
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 laser. For the oxide clusters V 4 O 9 − and V 4 O 10 − , the bands of the terminal vanadyl oxygen atoms, ν (VO t ), and of the bridging oxygen atoms, ν (VO 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 CO stretch, ν (CO). Density functional calculations are used as a complement for the experimental studies and the interpretation of the infrared spectra. The results depend in an unusual way on the functional employed (BLYP versus B3LYP), which is due to the presence of both VO(CH 3 ) single and VO double bonds as terminal bonds and to the strong multireference character of the latter.