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Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering

Authors :
Nimmrich, Amke
Panman, Matthijs R.
Berntsson, Oskar
Biasin, Elisa
Niebling, Stephan
Petersson, Jonas
Hoernke, Maria
Björling, Alexander
Gustavsson, Emil
van Driel, Tim B.
Dohn, Asmus O.
Laursen, Mads
Zederkof, Diana B.
Tono, Kensuke
Katayama, Tetsuo
Owada, Shigeki
Nielsen, Martin M.
Davidsson, Jan
Uhlig, Jens
Hub, Jochen S.
Haldrup, Kristoffer
Westenhoff, Sebastian
Nimmrich, Amke
Panman, Matthijs R.
Berntsson, Oskar
Biasin, Elisa
Niebling, Stephan
Petersson, Jonas
Hoernke, Maria
Björling, Alexander
Gustavsson, Emil
van Driel, Tim B.
Dohn, Asmus O.
Laursen, Mads
Zederkof, Diana B.
Tono, Kensuke
Katayama, Tetsuo
Owada, Shigeki
Nielsen, Martin M.
Davidsson, Jan
Uhlig, Jens
Hub, Jochen S.
Haldrup, Kristoffer
Westenhoff, Sebastian
Publication Year :
2023

Abstract

Resolving the structural dynamics of bond breaking, bond formation, and solvation is required for a deeper understanding of solutionphase chemical reactions. In this work, we investigate the photodissociation of triiodide in four solvents using femtosecond time-resolved X-ray solution scattering following 400 nm photoexcitation. Structural analysis of the scattering data resolves the solvent-dependent structural evolution during the bond cleavage, internal rearrangements, solvent-cage escape, and bond reformation in real time. The nature and structure of the reaction intermediates during the recombination are determined, elucidating the full mechanism of photodissociation and recombination on ultrafast time scales. We resolve the structure of the precursor state for recombination as a geminate pair. Further, we determine the size of the solvent cages from the refined structures of the radical pair. The observed structural dynamics present a comprehensive picture of the solvent influence on structure and dynamics of dissociation reactions.

Details

Database :
OAIster
Notes :
application/pdf, English
Publication Type :
Electronic Resource
Accession number :
edsoai.on1428019548
Document Type :
Electronic Resource
Full Text :
https://doi.org/10.1021.jacs.3c00484