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Title: Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering

Abstract

Resolving the structural dynamics of the initial steps of chemical reactions is challenging. We report the femtosecond time-resolved wide-angle x-ray scattering of the photodissociation of diiodomethane in cyclohexane. The data reveal with structural detail how the molecule dissociates into radicals, how the radicals collide with the solvent, and how they form the photoisomer. We extract how translational and rotational kinetic energy is dispersed into the solvent. We also find that 85% of the primary radical pairs are confined to their original solvent cage and discuss how this influences the downstream recombination reactions.

Authors:
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Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); German Research Foundation (DFG); European Research Council (ERC)
OSTI Identifier:
1724239
Alternate Identifier(s):
OSTI ID: 1768066
Grant/Contract Number:  
AC02-76SF00515; 279944; 6581802; HU 1971-1/1; HU 1971-3/1; HU 1971-4/1; 2016A8037
Resource Type:
Published Article
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Name: Physical Review Letters Journal Volume: 125 Journal Issue: 22; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical Physics & Physical Chemistry; Chemical reactions; Structural properties; Liquids; Configuration interaction; Molecular dynamics; X-ray diffuse scattering

Citation Formats

Panman, Matthijs R., Biasin, Elisa, Berntsson, Oskar, Hermann, Markus, Niebling, Stephan, Hughes, Ashley J., Kübel, Joachim, Atkovska, Kalina, Gustavsson, Emil, Nimmrich, Amke, Dohn, Asmus O., Laursen, Mads, Zederkof, Diana B., Honarfar, Alireza, Tono, Kensuke, Katayama, Tetsuo, Owada, Shigeki, van Driel, Tim B., Kjaer, Kasper, Nielsen, Martin M., Davidsson, Jan, Uhlig, Jens, Haldrup, Kristoffer, Hub, Jochen S., and Westenhoff, Sebastian. Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering. United States: N. p., 2020. Web. https://doi.org/10.1103/PhysRevLett.125.226001.
Panman, Matthijs R., Biasin, Elisa, Berntsson, Oskar, Hermann, Markus, Niebling, Stephan, Hughes, Ashley J., Kübel, Joachim, Atkovska, Kalina, Gustavsson, Emil, Nimmrich, Amke, Dohn, Asmus O., Laursen, Mads, Zederkof, Diana B., Honarfar, Alireza, Tono, Kensuke, Katayama, Tetsuo, Owada, Shigeki, van Driel, Tim B., Kjaer, Kasper, Nielsen, Martin M., Davidsson, Jan, Uhlig, Jens, Haldrup, Kristoffer, Hub, Jochen S., & Westenhoff, Sebastian. Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering. United States. https://doi.org/10.1103/PhysRevLett.125.226001
Panman, Matthijs R., Biasin, Elisa, Berntsson, Oskar, Hermann, Markus, Niebling, Stephan, Hughes, Ashley J., Kübel, Joachim, Atkovska, Kalina, Gustavsson, Emil, Nimmrich, Amke, Dohn, Asmus O., Laursen, Mads, Zederkof, Diana B., Honarfar, Alireza, Tono, Kensuke, Katayama, Tetsuo, Owada, Shigeki, van Driel, Tim B., Kjaer, Kasper, Nielsen, Martin M., Davidsson, Jan, Uhlig, Jens, Haldrup, Kristoffer, Hub, Jochen S., and Westenhoff, Sebastian. Tue . "Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering". United States. https://doi.org/10.1103/PhysRevLett.125.226001.
@article{osti_1724239,
title = {Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering},
author = {Panman, Matthijs R. and Biasin, Elisa and Berntsson, Oskar and Hermann, Markus and Niebling, Stephan and Hughes, Ashley J. and Kübel, Joachim and Atkovska, Kalina and Gustavsson, Emil and Nimmrich, Amke and Dohn, Asmus O. and Laursen, Mads and Zederkof, Diana B. and Honarfar, Alireza and Tono, Kensuke and Katayama, Tetsuo and Owada, Shigeki and van Driel, Tim B. and Kjaer, Kasper and Nielsen, Martin M. and Davidsson, Jan and Uhlig, Jens and Haldrup, Kristoffer and Hub, Jochen S. and Westenhoff, Sebastian},
abstractNote = {Resolving the structural dynamics of the initial steps of chemical reactions is challenging. We report the femtosecond time-resolved wide-angle x-ray scattering of the photodissociation of diiodomethane in cyclohexane. The data reveal with structural detail how the molecule dissociates into radicals, how the radicals collide with the solvent, and how they form the photoisomer. We extract how translational and rotational kinetic energy is dispersed into the solvent. We also find that 85% of the primary radical pairs are confined to their original solvent cage and discuss how this influences the downstream recombination reactions.},
doi = {10.1103/PhysRevLett.125.226001},
journal = {Physical Review Letters},
number = 22,
volume = 125,
place = {United States},
year = {2020},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1103/PhysRevLett.125.226001

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