Understanding electronic excited states in BiFeO3 via ab initio calculations and symmetry analysis

BiFeO3 3 is a technologically relevant multiferroic perovskite featuring ferroelectricity and antiferromagnetism. Its lattice, magnetic, and ferroelectric degrees of freedom are coupled to its optically active excitations and thus hold the potential to be reversibly probed and controlled by light. In this work, we combine ab initio density functional and many-body perturbation theory methods with an extensive symmetry and atomic-orbital analysis to describe and understand the electronic excited states spectrum and its imprint on the optical absorption spectrum with quantitative accuracy and qualitative insights. We find that the optical absorption spectrum of BiFeO3 3 contains several strongly bound and spatially localized electronic transitions in which the spin degree of freedom is flipped. We thoroughly characterize these localized spin-flip transitions in terms of the unusual crystal-field splitting of Fe-3d d single-electron orbitals. Our symmetry analysis further allows us to thoroughly explain how the spin content and the energetic fine structure of these strongly bound excitons are dictated by the interplay between crystal symmetry, electron-hole attraction, and the spin-orbit coupling.