학술논문
Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering
Document Type
Author
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
Source
Journal of the American Chemical Society NanoLund: Centre for Nanoscience. 145(29):15754-15765
Subject
Language
English
ISSN
0002-7863
Abstract
Resolving the structural dynamics of bond breaking, bond formation, and solvation is required for a deeper understanding of solution-phase 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.