A combined photoelectron-imaging spectroscopic and theoretical investigation on the electronic structure of the VO₂H anion

Abstract

The PES of VO2H− was detected at 814 nm. The electronic configuration of anionic and neutral of VO2H is 4A′′ and 3A′′, respectively. The electron was detached from the s-type 17a′ MO of the anionic ground state of VO2H.

Direct spectroscopic evidence for the high-spin state of dioxidomanganese(v)

“…From the electron configuration of the [OMn IV OH] + complex we deduce a 4 A′′ ( C s ) ground state, which is identical to the reported ground state of isoelectronic [OVOH] − . 61…”

“…From the electron configuration of the [OMn IV OH] + complex we deduce a 4 A 00 (C s ) ground state, which is identical to the reported ground state of isoelectronic [OVOH] À . 61 At the manganese site the local symmetry resembles neutral OMnO with similar Mn-O bond distances and angle of 1.603/ 1.699 Å, 123.51 in [OMn IV OH] + compared to 1.639 Å, 118.41 13 and 1.581 Å, 1311 62 in neutral OMnO. In C 2v symmetry the ground state of the [OMn IV OH] + complex could be described as a 4 B 1 state with (10a 1 ) 1 (4b 1 ) 1 (11a 1 ) 1 configuration, in agreement with the ground state reported for neutral OMnO by DFT, 52,53,56,62 but distinct from a 4 B 2 ground state found by employing multiconfigurational wavefunction methods.…”