A spin-selective and polarization dependent study at the K absorption pre-edge in hematite (alpha-Fe2O3) was performed by means of 1s3p resonant x-ray emission spectroscopy on a single crystal. The experimental results can be modeled using a band structure approach [local density approximation (LDA+U)]. The spin-selective spectra in connection with the calculations firmly establish metal-oxygen and metal-metal orbital hybridizations. A phase shift in the polarization dependent absorption cross section is observed between the first two absorption features showing directionality in the orbital hybridization.
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