Chemical dependence of interatomic X-ray transition energies and intensities – a study of Mn Kβ″ and Kβ2, 5 spectra

A study of ligand (N, O, F) 2s to metal (Mn) 1s `interatomicʹ or `crossoverʹ X-ray transitions is reported. We show that the energy of the Kβ″ feature is related to the ligand 2s binding energy and can be used to identify the type of ligand. For oxygen-ligated Mn compounds, the strength of the Kβ″ transition decreases exponentially with increasing Mn–O distance. This can be used to predict distances to ∼0.1 Å. The Kβ2, 5 energy shows shifts of ∼1 eV per unit oxidation state. Kβ″ and Kβ2, 5 transitions are a promising tool for structural characterization of transition-metal complexes.