Metal-water covalency in the photo-aquated ferrocyanide complex as seen by multi-edge picosecond X-ray absorption

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Abstract

In this work, we investigate the photo-aquation reaction of the ferrocyanide anion with multi-edge picosecond soft X-ray spectroscopy. Combining the information of the iron L-edge with nitrogen and oxygen K-edges, we carry out a complete characterization of the bonding channels in the [Fe(CN)5(H2O)]3− photo-product. We observe clear spectral signatures of covalent bonding between water and the metal, reflecting the mixing of the Fe dz2 orbital with the 3a1 and 4a1 orbitals of H2O. Additional fingerprints related to the symmetry reduction and the resulting loss in orbital degeneracy are also reported. The implications of the elucidated fingerprints in the context of future ultra-fast experiments are also discussed.

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Vaz da Cruz, V., Mascarenhas, E. J., Büchner, R., Jay, R. M., Fondell, M., Eckert, S., & Föhlisch, A. (2022). Metal-water covalency in the photo-aquated ferrocyanide complex as seen by multi-edge picosecond X-ray absorption. Physical Chemistry Chemical Physics, 24(45), 27819–27826. https://doi.org/10.1039/d2cp04084k

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