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

Marco Reinhard (), Alessandro Gallo, Meiyuan Guo, Angel T. Garcia-Esparza, Elisa Biasin, Muhammad Qureshi, Alexander Britz, Kathryn Ledbetter, Kristjan Kunnus, Clemens Weninger, Tim Driel, Joseph Robinson, James M. Glownia, Kelly J. Gaffney, Thomas Kroll, Tsu-Chien Weng, Roberto Alonso-Mori () and Dimosthenis Sokaras ()
Additional contact information
Marco Reinhard: SLAC National Accelerator Laboratory
Alessandro Gallo: SLAC National Accelerator Laboratory
Meiyuan Guo: SLAC National Accelerator Laboratory
Angel T. Garcia-Esparza: SLAC National Accelerator Laboratory
Elisa Biasin: Pacific Northwest National Laboratory
Muhammad Qureshi: SLAC National Accelerator Laboratory
Alexander Britz: SLAC National Accelerator Laboratory
Kathryn Ledbetter: Stanford University
Kristjan Kunnus: SLAC National Accelerator Laboratory
Clemens Weninger: SLAC National Accelerator Laboratory
Tim Driel: SLAC National Accelerator Laboratory
Joseph Robinson: SLAC National Accelerator Laboratory
James M. Glownia: SLAC National Accelerator Laboratory
Kelly J. Gaffney: SLAC National Accelerator Laboratory
Thomas Kroll: SLAC National Accelerator Laboratory
Tsu-Chien Weng: ShanghaiTech University
Roberto Alonso-Mori: SLAC National Accelerator Laboratory
Dimosthenis Sokaras: SLAC National Accelerator Laboratory

Nature Communications, 2023, vol. 14, issue 1, 1-11

Abstract: Abstract Reliably 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.

Date: 2023
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DOI: 10.1038/s41467-023-37922-x

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