Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first-principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge-transfer bands and thereby evidence for strong σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.
Soft X-ray absorption and resonant inelastic X-ray scattering at the Mn Ledge are established as tools for gaining electronic structural insights into water oxidation catalysis. The MnO x catalyst with the lowest d-d transitions, strongest charge transfer and a higher proportion of Mn 3+ over Mn 2+/4+ produces itinerant electrons that contribute to a higher catalytic activity.
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