The structure and property prediction of metal oxides can significantly be improved by incorporating exact Hartree-Fock (HF) exchange into density functional theory (DFT), which is the so-called hybrid DFT. We explored the impact of HF exchange inclusion on the predicted structural, bonding, and electronic properties of bismuth vanadate (BiVO${}_4$), with particular attention to the difference between its monoclinic and tetragonal scheelite phases. The applied exchange-correlation (xc) functionals include the gradient corrected Perdew-Burke-Ernzerhof (PBE) and the PBE-HF hybrid functionals with HF exchange amounts of 10$\%$, 25$\%$, and 50$\%$. We find that the PBE-HF25$\%$ yields a monoclinic structure in very close agreement with the experimentally determined structure, while the PBE-HF50$\%$ tends to overestimate the monoclinic distortion and the PBE/PBE-HF10$\%$ can hardly identify a distinct monoclinic configuration at ambient conditions. Electronic structure analysis reveals that the increasing monoclinic distortion with the amount of HF exchange is related to the enhancement of hybridization between Bi 6$s$-O 2$p$ antibonding states and unoccupied Bi 6$p$ states. The bonding mechanisms and band structures of the monoclinic and tetragonal phases of BiVO${}_4$ were also investigated, and we discuss how the predictions are sensitive to the xc functional choice.

• Received 7 July 2012

DOI:https://doi.org/10.1103/PhysRevB.86.165209