Electron and Hole Mobilities in Bulk Hematite from Spin-Constrained Density Functional Theory

[Image: see text] Transition metal oxide materials have attracted much attention for photoelectrochemical water splitting, but problems remain, e.g. the sluggish transport of excess charge carriers in these materials, which is not well understood. Here we use periodic, spin-constrained and gap-optimized hybrid density functional theory to uncover the nature and transport mechanism of holes and excess electrons in a widely used water splitting material, bulk-hematite (α-Fe(2)O(3)). We find that upon ionization the hole relaxes from a delocalized band state to a polaron localized on a single iron atom with localization induced by tetragonal distortion of the six surrounding iron–oxygen bonds. This distortion is responsible for sluggish hopping transport in the Fe-bilayer, characterized by an activation energy of 70 meV and a hole mobility of 0.031 cm(2)/(V s). By contrast, the excess electron induces a smaller distortion of the iron–oxygen bonds resulting in delocalization over two neighboring Fe units. We find that 2-site delocalization is advantageous for charge transport due to the larger spatial displacements per transfer step. As a result, the electron mobility is predicted to be a factor of 3 higher than the hole mobility, 0.098 cm(2)/(V s), in qualitative agreement with experimental observations. This work provides new fundamental insight into charge carrier transport in hematite with implications for its photocatalytic activity.