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

Nimmrich, Amke ; Panman, Matthijs R. ; Berntsson, Oskar ; Biasin, Elisa ; Niebling, Stephan ; Petersson, Jonas ; Hoernke, Maria ; Björling, Alexander LU ; Gustavsson, Emil and van Driel, Tim B. , et al. (2023) In Journal of the American Chemical Society 145(29). p.15754-15765
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... (More)

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.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
145
issue
29
pages
12 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:37163700
  • scopus:85160799905
ISSN
0002-7863
DOI
10.1021/jacs.3c00484
language
English
LU publication?
yes
id
f05a15a9-8638-49a3-aa67-2fbc160bfd10
date added to LUP
2023-09-15 11:29:28
date last changed
2024-04-20 03:24:45
@article{f05a15a9-8638-49a3-aa67-2fbc160bfd10,
  abstract     = {{<p>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.</p>}},
  author       = {{Nimmrich, Amke and Panman, Matthijs R. and Berntsson, Oskar and Biasin, Elisa and Niebling, Stephan and Petersson, Jonas and Hoernke, Maria and Björling, Alexander and Gustavsson, Emil and van Driel, Tim B. and Dohn, Asmus O. and Laursen, Mads and Zederkof, Diana B. and Tono, Kensuke and Katayama, Tetsuo and Owada, Shigeki and Nielsen, Martin M. and Davidsson, Jan and Uhlig, Jens and Hub, Jochen S. and Haldrup, Kristoffer and Westenhoff, Sebastian}},
  issn         = {{0002-7863}},
  language     = {{eng}},
  month        = {{07}},
  number       = {{29}},
  pages        = {{15754--15765}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of the American Chemical Society}},
  title        = {{Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering}},
  url          = {{http://dx.doi.org/10.1021/jacs.3c00484}},
  doi          = {{10.1021/jacs.3c00484}},
  volume       = {{145}},
  year         = {{2023}},
}