Negative ion photoelectron spectra simulation of V3O from a density functional study

Abstract

A density functional study of neutral and anionic vanadium trimer monoxides is 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 in order to determine the ground state structures. For both systems a planar C2v structure with an edge-bonded oxygen atom was found as the ground state. Equilibrium structure parameters of ground states as well as low-lying excited states, harmonic frequencies, the adiabatic electron affinity, and Kohn–Sham orbital diagrams are reported. The experimental negative ion photoelectron spectra of V3O was simulated by calculating multidimensional Franck–Condon factors, using the geometries and harmonic frequencies of the calculated ground states of V3O− and V3O. The good agreement between the experimental and the theoretical spectra allows the determination of the ground state structure of V3O and V3O−. This represents the first work in which a simulation of a vibrationally resolved negative ion photoelectron spectra of a transition metal oxide is presented.