On the electronic structure of transition-metal oxide cations:DFTCalculations for VO⁺ and MoO⁺

Two transition-metal oxide diatomic cations, VO⁺ and MoO⁺ are considered in this article. Ground- and excited-state properties of the cations are derived from spin-polarized DF calculations, including spectroscopic constants and metal–oxygen bonding features. A set of ionization potentials are calculated and, for vanadium oxide, compared with photoelectron spectroscopy data and a few available ab initio calculations. All calculated properties are close to experiment, the agreement being much better than for other traditional quantum chemical calculations. Present results together with our earlier findings for neutral molecules provide an excellent confirmation of the good performance of DFT in the case of transition-metal systems. © 1995 John Wiley & Sons, Inc.