An electron spin resonance investigation of vanadium dioxide (51V16O2 and 51V17O2) and 51V17O in neon matrices with preliminary assignments for VO3 and V+2: Comparison with ab initio theoretical calculations

Abstract

The first spectroscopic characterization of the VO2 radical is reported along with new results for V17O and tentative assignments for the VO3 and V+2 radicals. These vanadium radicals were investigated in neon matrices at 4 K by electron spin resonance utilizing conventional high temperature vaporization and pulsed laser ablation generation methods. A detailed ESR study of VO2 showed it to be nonlinear with a 2A1 ground state; the g tensor analysis reveals the presence of an excited electronic state (2B1) approximately 1 eV above the ground state. This excited state prediction and the observed nuclear hyperfine interactions (A tensors) for 51V and 17O were compared with theoretical results obtained from various ab initio computational methods. Ab initio calculations with an extended basis set were performed at various levels of theory including UHF, ROHF, CAS-SCF, and MR-SDCI (multireference single and double configuration interaction). While UHF calculations of the hyperfine interaction were grossly in error, the better levels of theory gave qualitative agreement with experiment and provided an aid to interpretation. VO2 is predicted to be a bent 2A1 state, correlating with the linear 2Δ configuration having the odd electron predominantly in the V 3d orbital. VO3 is predicted to be planar C2v, with the odd electron in a b2 orbital localized in the oxygen in-plane n-type p orbitals.

A systematic study of neutral and charged 3d-metal trioxides and tetraoxides

“…Our results are; however, different for VO 3 and CoO 3. The former neutral was previously found to have a trigonal planar geometry of C 2v symmetry 51 while we obtained a slightly distorted D 3h nonplanar geometry of C 3v geometry, in agreement with the results of previous DFT-GGA (Ref. 52) and quantum Monte-Carlo 53 calculations.…”

Mass‐selective vibrational spectroscopy of vanadium oxide cluster ions

“…Initial studies focused on the diatomic VO (Keenan & Schroeder, 1952;Lagerqvist & Selin, 1957), motivated by its near infrared emission in the spectra of M-type stars. VO has a 4 S À ground state (Kasai, 1968;Knight et al, 1996) with fundamental constants o 0 ¼ 1001.8 cm À1 and r 0 ¼ 1.592 Å in the gas phase (Merer, 1989). Formal removal of an electron from the vanadium 4s orbital leads to VO þ in its 3 S À ground state and a strengthening of the V=O bond (o 0 ¼ 1060 AE 40 cm À1 , r 0 ¼ 1.56 Å ) (Dyke et al, 1985;Harrington & Weisshaar, 1992).…”

Electron spin resonance studies of199HgH,201HgH,199HgD and201HgD isolated in neon and argon matrices at 4K: an electronic structure investigation

“…The most desirable approach is to evaluate A,,, and Adlp directly from a computed wavefunction-the strategy employed for numerous light-atom radical (neutrals and ions) studies conducted in collaboration with Professor E. R. Davidson and his associates using their MELDF program [21]. Recent examples include VOz [22], ScO [23] and ZnH [24].…”