Anion photoelectron spectroscopy was used to study small negatively charged vanadium oxide clusters at 4.66 eV photon energy. The electronic structure of the vanadium clusters was investigated as a function of size n and composition m. The changes of the electronic structure of the vanadium cluster cores after adding two oxygen atoms were examined. Thermomechanical cycles were used to determine relative dissociation energies for different oxygen-loss channels from the parent clusters. Electron affinities and vertical detachment energies were found to increase with increasing cluster size.
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