Structures and vibrations of V3O and V3O-:: A density functional study

Density functional calculations of neutral and anionic vanadium trimer monoxide are presented. The calculations were of all-electron type, employing a newly developed basis set for the vanadium atom. Different isomers of V3O and V3O- were studied to determine the ground-state structures. For both systems, a planar C-2v structure with an edge-bound oxygen atom was found as ground state. Equilibrium-structure parameters, harmonic frequencies, adiabatic electron affinity and Kohn-Sham orbital diagrams are reported. The calculated values are in good agreement with the available experimental data obtained from negative ion photoelectron spectroscopy. The correlation diagram between the neutral and anionic V3O shows that, in agreement with the experimental prediction, the extra electron in the anionic system occupies a nonbonding orbital. (C) 2002 Wiley Periodicals, Inc.