First-principles FP-LAPW calculations and X-ray spectroscopy studies of the electronic structure of Zr3V3O and Zr3V3O0.6 oxides

Electronic properties of Zr3V3O oxide, a very promising hydrogen-storage material, were studied both from theoretical and experimental points of view employing the full potential linearized augmented plane wave (FP-LAPW) method as well as X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES). Total and partial densities of states of the constituting atoms of Zr3V3O have been derived from the FP-LAPW calculations. These data indicate that, the O 2p-like states are the dominant contributors in the bottom of the valence band, whilst the top of the valence band and the bottom of the conduction band of Zr3V3O are dominated by contributions of the V2 3d-like states, with slightly smaller contributions of the V1 3d-like states as well. Significant contributions of the Zr 4d-like states throughout the whole valence-band region and near the bottom of the conduction band are also characteristic of the electronic structure of Zr3V3O. The XPS valence-band spectra and the XES Zr Lβ2,15, V Lα and O Kα bands have been derived and compared on a common energy scale for Zr3V3O and Zr3V3O0.6 oxides. This comparison of the experimental spectra was found to be in excellent agreement with the results of the FP-LAPW calculations. In addition, the XPS Zr 3d, V 2p and O 1s core-level binding energies have been measured for Zr3V3O and Zr3V3O0.6 oxides.

► Total and partial densities of states of the constituting atoms of Zr3V3O are calculated.
► O 2p states are the dominant contributors in the bottom of the valence band.
► The top of the valence band is dominated by contributions of the V 3d-like states.
► Contributions of V 3d states dominate at the bottom of the conduction band.
► The theoretical results have been confirmed experimentally.