First-principles study on the electronic and optical properties of Bi2WO6

Abstract

Photocatalytic materials attract continued scientific interest due to their possible application in energy harvesting. These applications critically rely on efficient photon absorption and exciton physics, which are governed by the underlying electronic structure. We report the electronic properties and optical response of the Bi₂WO₆ bulk photocatalyst using first-principle methods. The density functional theory DFT-computed electronic band gap is corrected by including Hubbard potentials for W-5d and O-2p orbitals, and one of the most advanced methods, Quasi-Particle (QP) GW at different levels, with semi-core states of Bi (5s and 5p) and W (4f), carefully taken into account in GW calculations. The perplexing nature of band character of Bi₂WO₆ is examined, and it comes out to be direct at PBE level without SOC. However, it shows indirect nature at GW level or when Spin–Orbit Coupling (SOC) is turned on even at PBE level. The optical response of the material system is computed within independent-particle approximation (IPA), taking into account local field effects and employing the time-dependent DFT (TDDFT) method. Bethe–Salpeter equation (BSE) is used to capture the excitonic effect, and the results of these approximations are compared with the experimental data. Our first-principle calculations results indicate that electron–hole interaction significantly modifies optical absorption of Bi₂WO₆, thereby verifying the reported experimental observations.