X-ray Absorption Linear Dichroism at the Ti K-edge of TiO2 anatase single crystal

Anatase TiO2 (a-TiO2) exhibits a strong X-ray absorption linear dichroism with the X-ray incidence angle in the pre-edge, the XANES and the EXAFS at the titanium K-edge. The strong p-orbital polarization and strong p - d orbital mixing in the pre-edge is the cause of this effect. An unambiguous assignment of the pre-edge peak transitions is made in the monoelectronic approximation with the support of ab initio finite difference method calculations and spherical tensor analysis in quantitative agreement with the experiment. Peak A2 which was previously assigned to a transition involving pentacoordinated titanium atoms exhibits a quadrupolar angular evolution with incidence angle. These results pave the way to the use of the pre-edge peaks at the K-edge of a-TiO2 to characterize the electronic structure of related materials and in the field of ultrafast XAS where the linear dichroism can be used to compare the photophysics along different axes.