Ab Initio Calculations of Electronic Properties of Vanadium Oxides

In this comprehensive study, we have performed one-electron Kohn–Sham electronic band-structure calculations of VO₂, V₂O₃ and V₂O₅ in both metallic and insulating phases, implementing a full ab initio simulation package based on Density Functional Theory, Plane Waves and Pseudopotentials (PPs). Electronic band structures are found to be influenced by crystal structure, crystal field splitting and strong hybridization between O₂p and V₃d bands. “Intermediate bands”, with narrow band widths, lying just below the higher conduction bands, are observed in V₂O₅. Similar calculations are performed for both metallic and insulating phases of bulk VO₂ and V₂O₃. Unlike in the metallic phase, bands corresponding to “valence electrons” considered in the PPs are found to be fully occupied in the insulating phases.