Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy

Author:

Reinhard MarcoORCID,Gallo AlessandroORCID,Guo MeiyuanORCID,Garcia-Esparza Angel T.ORCID,Biasin ElisaORCID,Qureshi Muhammad,Britz Alexander,Ledbetter KathrynORCID,Kunnus Kristjan,Weninger Clemens,van Driel Tim,Robinson Joseph,Glownia James M.,Gaffney Kelly J.ORCID,Kroll Thomas,Weng Tsu-Chien,Alonso-Mori RobertoORCID,Sokaras DimosthenisORCID

Abstract

AbstractReliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kβ main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kβ main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

Publisher

Springer Science and Business Media LLC

Subject

General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry,Multidisciplinary

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