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

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.

Gallo, AlessandroStanford Linear Accelerator Center (SLAC) (author)
Guo, MeiyuanStanford Linear Accelerator Center (SLAC) (author)
Garcia-Esparza, Angel T.Stanford Linear Accelerator Center (SLAC) (author)
Biasin, ElisaPacific Northwest National Laboratory (author)
Qureshi, MuhammadStanford Linear Accelerator Center (SLAC) (author)
Britz, AlexanderStanford Linear Accelerator Center (SLAC) (author)
Ledbetter, KathrynHarvard University,Stanford University (author)
Kunnus, KristjanStanford Linear Accelerator Center (SLAC) (author)
Weninger, ClemensLund University,Lunds universitet,MAX IV, Vetenskaplig Data,MAX IV, Tekniska divisionen,MAX IV-laboratoriet,MAX IV, Scientific Data,MAX IV, Technical division,MAX IV Laboratory,Stanford Linear Accelerator Center (SLAC)(Swepub:lu)cl1816we (author)
van Driel, TimStanford Linear Accelerator Center (SLAC) (author)
Robinson, JosephStanford Linear Accelerator Center (SLAC) (author)
Glownia, James M.Stanford Linear Accelerator Center (SLAC) (author)
Gaffney, Kelly J.Stanford Linear Accelerator Center (SLAC) (author)
Kroll, ThomasStanford Linear Accelerator Center (SLAC) (author)
Weng, Tsu ChienShanghaiTech University (author)
Alonso-Mori, RobertoStanford Linear Accelerator Center (SLAC) (author)
Sokaras, DimosthenisStanford Linear Accelerator Center (SLAC) (author)
Stanford Linear Accelerator Center (SLAC)Pacific Northwest National Laboratory (creator_code:org_t)

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Physical Chemist ...

Kungliga biblioteket hanterar dina personuppgifter i enlighet med EU:s dataskyddsförordning (2018), GDPR. Läs mer om hur det funkar här.
Så här hanterar KB dina uppgifter vid användning av denna tjänst.