A photoelectron spectroscopic study of monovanadium oxide anions (VO{sub x}{sup {minus}}, x=1{endash}4)
- Department of Physics, Washington State University, Richland, Washington99352 (United States)
We report on a photoelectron spectroscopic study of monovanadium oxides, VO{sub x}{sup {minus}} (x=1{endash}4), at four photon energies: 532, 355, 266, and 193 nm. Vibrationally resolved spectra are obtained for VO{sup {minus}} at 532 and 355 nm detachment photon energies. Two new low-lying excited states are observed for VO at 5630 and 14920cm{sup {minus}1} above the ground state. These states are assigned to two doublet states, {sup 2}{Sigma}{sup {minus}} and {sup 2}{Phi}, respectively. The 532 and 355 nm spectra of VO{sub 2}{sup {minus}} reveal a single vibrational progression for the ground state with a frequency of 970cm{sup {minus}1} ({nu}{sub 1}). Three electronic excited states are observed for VO{sub 2} in the 193 nm spectrum. For VO{sub 3}{sup {minus}}, three surprisingly sharp detachment transitions are observed at 193 nm. The two excited states of VO{sub 3} are measured to be 0.59 and 0.79 eV above the ground state. The spectra of VO{sub 2}{sup {minus}} and VO{sub 3}{sup {minus}} are interpreted using the molecular-orbital schemes obtained in a recent {ital ab initio} theoretical study [Knight, Jr. {ital et al.}, J. Chem. Phys. {bold 105}, 10237 (1996)], which predicts that both VO{sub 2} and VO{sub 3} neutrals are of C{sub 2v} symmetry with a doublet ground state. The spectrum of VO{sub 4}{sup {minus}} is obtained at 193 nm, showing features similar to that of VO{sub 3}{sup {minus}}, but much more broadened. The adiabatic electron affinities of VO, VO{sub 2}, VO{sub 3}, and VO{sub 4} are measured to be 1.229 (8), 2.03 (1), 4.36 (5), and 4.0 (1) eV, respectively, with a significant increase from VO{sub 2} to VO{sub 3}. The electronic and geometrical structures of the series of monovanadium oxide species are discussed based on the current observation and previous spectroscopic and theoretical results. {copyright} {ital 1998 American Institute of Physics.}
- OSTI ID:
- 615392
- Journal Information:
- Journal of Chemical Physics, Vol. 108, Issue 13; Other Information: PBD: Apr 1998
- Country of Publication:
- United States
- Language:
- English
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