1. The spectrum of an octahedral molecule in a degenerate electronic state: The ν[sub 6] fundamental band of jet-cooled V(CO)[sub 6].
- Author
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Rey, M., Boudon, V., Loe¨te, M., Asselin, P., Soulard, P., and Manceron, L.
- Subjects
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FOURIER transform infrared spectroscopy , *VANADIUM , *CARBONYL compounds , *TENSOR algebra , *ANALYTICAL chemistry - Abstract
The jet-cooled FTIR spectrum of the ν[sub 6] fundamental band (C-O stretch) of vanadium hexacarbonyl, V(CO)[sub 6], is studied for the first time. The spectrum shows a very unusual structure consisting of three well-defined broad subbands, without the usual PQR structure. V(CO)[sub 6] being an open-shell system this is attributed to a dynamical F[sub 2g]xF[sub 1u] Jahn-Teller coupling which considerably complicates the analysis. A new theoretical model based on group theory and tensorial algebraic techniques is developed in this paper for the very first attempt to analyze such a rovibronic spectrum. The assumption of a negligible spin-orbit coupling is validated by the overall agreement between predicted and observed band profiles. The rovibronic Hamiltonian and dipole moment operators have been expanded in order to enable a simultaneous treatment of the four vibronic sublevels. We were able to satisfactorily reproduce the band profile and thus to give the first estimation of some rovibronic parameters for this molecule. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]
- Published
- 2001
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