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

Author

Listed:
  • 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
    Harvard University)

  • Kristjan Kunnus

    (SLAC National Accelerator Laboratory)

  • Clemens Weninger

    (SLAC National Accelerator Laboratory
    Lund University)

  • 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)

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.

Suggested Citation

  • Marco Reinhard & Alessandro Gallo & Meiyuan Guo & Angel T. Garcia-Esparza & Elisa Biasin & Muhammad Qureshi & Alexander Britz & Kathryn Ledbetter & Kristjan Kunnus & Clemens Weninger & Tim Driel & Jos, 2023. "Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
  • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-37922-x
    DOI: 10.1038/s41467-023-37922-x
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    References listed on IDEAS

    as
    1. Tim B. van Driel & Kasper S. Kjær & Robert W. Hartsock & Asmus O. Dohn & Tobias Harlang & Matthieu Chollet & Morten Christensen & Wojciech Gawelda & Niels E. Henriksen & Jong Goo Kim & Kristoffer Hald, 2016. "Atomistic characterization of the active-site solvation dynamics of a model photocatalyst," Nature Communications, Nature, vol. 7(1), pages 1-7, December.
    2. Wenkai Zhang & Roberto Alonso-Mori & Uwe Bergmann & Christian Bressler & Matthieu Chollet & Andreas Galler & Wojciech Gawelda & Ryan G. Hadt & Robert W. Hartsock & Thomas Kroll & Kasper S. Kjær & Kath, 2014. "Tracking excited-state charge and spin dynamics in iron coordination complexes," Nature, Nature, vol. 509(7500), pages 345-348, May.
    3. Marco E. Reinhard & Michael W. Mara & Thomas Kroll & Hyeongtaek Lim & Ryan G. Hadt & Roberto Alonso-Mori & Matthieu Chollet & James M. Glownia & Silke Nelson & Dimosthenis Sokaras & Kristjan Kunnus & , 2021. "Short-lived metal-centered excited state initiates iron-methionine photodissociation in ferrous cytochrome c," Nature Communications, Nature, vol. 12(1), pages 1-8, December.
    4. Md. Wahadoszamen & Iris Margalit & Anjue Mane Ara & Rienk van Grondelle & Dror Noy, 2014. "The role of charge-transfer states in energy transfer and dissipation within natural and artificial bacteriochlorophyll proteins," Nature Communications, Nature, vol. 5(1), pages 1-8, December.
    5. Kristjan Kunnus & Morgane Vacher & Tobias C. B. Harlang & Kasper S. Kjær & Kristoffer Haldrup & Elisa Biasin & Tim B. Driel & Mátyás Pápai & Pavel Chabera & Yizhu Liu & Hideyuki Tatsuno & Cornelia Tim, 2020. "Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering," Nature Communications, Nature, vol. 11(1), pages 1-11, December.
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