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

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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 laserablation generation methods. A detailed ESR study of VO2 showed it to be nonlinear with a 2 A 1ground state; the gtensor analysis reveals the presence of an excited electronic state (2 B 1) approximately 1 eV above the ground state. This excited state prediction and the observed nuclear hyperfine interactions (Atensors) 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 2 A 1 state, correlating with the linear 2Δ configuration having the odd electron predominantly in the V 3d orbital. VO3 is predicted to be planar C 2v , with the odd electron in a b 2 orbital localized in the oxygen in‐plane n‐type p orbitals.