Interplay between Electronic Structure, Chemical Bonding, and Lattice Symmetry in Bismuth Vanadate

Abstract

Bismuth vanadate (BiVO$_4$) is a prototypical oxide photocatalyst that occurs in both tetragonal and monoclinic scheelite phases with markedly different photocatalytic and photoelectrochemical activities. Accurately identifying the monoclinic phase as the ground state and explaining the origin of its symmetry-breaking distortion are unusually challenging from a theoretical perspective, with various levels of theory and associated physical interpretations for this behaviour reported in the literature. Here, we resolve these discrepancies by systematically assessing the role of exact exchange with and without spin-orbit coupling, demonstrating that an accurate treatment of electronic localization is essential to stabilize the monoclinic scheelite structure. Using this framework, we compute the electronic band structure through dense sampling of the Brillouin zone and show that the band edges in monoclinic and tetragonal BiVO$_4$ lie far from conventional high-symmetry paths, leading to substantial differences in band gaps and carrier effective masses. Choosing the exchange-correlation functional that best reproduces the crystal structure leads to excellent predictions of the band gap once excitonic and thermal effects are taken into account. In addition, we show that the monoclinic distortion is driven by charge transfer between non-equivalent oxygen sites, which breaks the lattice symmetry and is suppressed by self-interaction errors when using semi-local DFT. These results establish a direct connection between the exchange-correlation functional, electronic localization, chemical bonding, and structural stability in BiVO$_4$, providing a foundation for robust ab initio descriptions of phase stability and optoelectronic properties in such complex oxides.