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A comprehensive approach to understanding the electronic structure of monoclinic scheelite bismuth vanadate (ms-BiVO₄), including both valence band (VB) and conduction band (CB) orbital character, is presented. Density functional theory (DFT) calculations are directly compared to experimental data obtained via X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy, resonant inelastic X-ray spectroscopy (RIXS), and X-ray photoelectron spectroscopy to provide a complete portrait of the total and partial density of states (DOS) near the bandgap. DFT calculations are presented to confirm the VB maximum and CB minimum are comprised primarily of O 2p and V 3d orbitals, respectively. Predicted triplet d-manifold splitting of V 3d CB states, arising from lone pair-induced lattice distortions, is quantified by V L- and O K-edge XAS. Furthermore, the partial contributions to the total DOS within both the CB …