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

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.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [4];  [2];  [2];  [5]; ORCiD logo [5];  [6]; ORCiD logo [2];  [3]; ORCiD logo [7]; ORCiD logo [8] more »;  [2];  [9] « less
+ Show Author Affiliations
  1. Department of Chemistry and Molecular Biology, University of Gothenburg, Box 462, 40530 Gothenburg, Sweden
  2. Department of Physics, Technical University of Denmark, 2800 Lyngby, Denmark
  3. Department of Chemistry, Ångström Laboratory, Uppsala University, Box 523, 75120 Uppsala, Sweden
  4. Department of Physics, Technical University of Denmark, 2800 Lyngby, Denmark, Faculty of Physical Sciences, University of Iceland, VR-III, 107 Reykjavík, Iceland
  5. Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan
  6. RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan
  7. Department of Chemical Physics, Lund University, Box 124, 22100 Lund, Sweden
  8. Georg-August-Universität Göttingen, Institute for Microbiology and Genetics, Justus-von-Liebig-Weg 11, 37077 Göttingen, Germany
  9. Department of Chemistry and Molecular Biology, University of Gothenburg, Box 462, 40530 Gothenburg, Sweden, Department of Chemical Physics, Lund University, Box 124, 22100 Lund, Sweden
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); German Research Foundation (DFG); Japan Society for the Promotion of Science (JSPS) (KAKENHI); Icelandic Research Fund; European Union (EU); Danish Council for Independent Research; European Research Council (ERC)
OSTI Identifier:
1973174
Alternate Identifier(s):
OSTI ID: 1989949; OSTI ID: 2005170
Report Number(s):
PNNL-SA-190436
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
AC02-76SF00515; HU 1971/1-1; HU 1971/3-1; HU 1971/4-1; JP19H05782; JP21H04974; JP21K18944; 196279-051; FP7-PEOPLE-2013-IEF 624864; DFF-8021-00347B; 6581802; 279944; AC05-76RL01830
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 145 Journal Issue: 29; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
chemical structure; ethanol; recombination; scattering; solvents; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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, and Westenhoff, Sebastian. Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering. United States: N. p., 2023. Web. doi:10.1021/jacs.3c00484.
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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. Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering. United States. https://doi.org/10.1021/jacs.3c00484
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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, and Westenhoff, Sebastian. Wed . "Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering". United States. https://doi.org/10.1021/jacs.3c00484.
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@article{osti_1973174,
title = {Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering},
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},
abstractNote = {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.},
doi = {10.1021/jacs.3c00484},
journal = {Journal of the American Chemical Society},
number = 29,
volume = 145,
place = {United States},
year = {Wed May 10 00:00:00 EDT 2023},
month = {Wed May 10 00:00:00 EDT 2023}
}
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