Importance of the Hubbard U parameter to explore accurate electronic and optical behaviour of BiFeO3

Abstract Based upon Hubbard U corrected density functional theory (DFT), the electronic and optical responses of multiferroic Bismuth ferrite (BiFeO 3 ; BFO) have been critically explored. Treating BFO as a strongly correlated insulating system, a Hubbard U parameter is considered for accurate description of localised Fe-3 d states. However, the U parameter for the Fe-3 d state is not sufficient as 2 p states of O atoms are greatly influenced by Fe-3 d states. Similar U parameters for Fe-3 d as well as O-2 p states are considered. An effective U value around 4.3 eV not only solves the band gap mismatch of BFO from both a theoretical and experimental aspect, but also predicts the exact nature of the band gap. Moreover, within this framework, the optical responses of BFO are critically investigated. Multiple transitions appearing in both theoretical and experimental absorption spectra are well explained by crystal field transitions of Fe 3+ ions in a d 5 high spin state, supported by the density of states curve of BFO. Therefore, based upon the DFT + U approach, accurate electronic and optical characteristics of BFO are critically explored, which is essential for its multidirectional application perspectives.