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

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

doi:10.1021/jacs.3c00484

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

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

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	15754-15765
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	145
Issue number	29
DOIs	https://doi.org/10.1021/jacs.3c00484
Publication status	Published - 2023 Jul 26

Subject classification (UKÄ)

Physical Chemistry (including Surface- and Colloid Chemistry)
Atom and Molecular Physics and Optics
Theoretical Chemistry (including Computational Chemistry)

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Nimmrich, A., Panman, M. R., Berntsson, O., Biasin, E., Niebling, S., Petersson, J., Hoernke, M., Björling, A., Gustavsson, E., van Driel, T. B., Dohn, A. O., Laursen, M., Zederkof, D. B., Tono, K., Katayama, T., Owada, S., Nielsen, M. M., Davidsson, J., Uhlig, J., ... Westenhoff, S. (2023). Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering. Journal of the American Chemical Society, 145(29), 15754-15765. https://doi.org/10.1021/jacs.3c00484

@article{f05a15a9863849a3aa672fbc160bfd10,

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.",

author = "Amke Nimmrich and Panman, \{Matthijs R.\} and Oskar Berntsson and Elisa Biasin and Stephan Niebling and Jonas Petersson and Maria Hoernke and Alexander Bj{\"o}rling and Emil Gustavsson and \{van Driel\}, \{Tim B.\} and Dohn, \{Asmus O.\} and Mads Laursen and Zederkof, \{Diana B.\} and Kensuke Tono and Tetsuo Katayama and Shigeki Owada and Nielsen, \{Martin M.\} and Jan Davidsson and Jens Uhlig and Hub, \{Jochen S.\} and Kristoffer Haldrup and Sebastian Westenhoff",

year = "2023",

month = jul,

day = "26",

doi = "10.1021/jacs.3c00484",

language = "English",

volume = "145",

pages = "15754--15765",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "The American Chemical Society (ACS)",

number = "29",

}

Nimmrich, A, Panman, MR, Berntsson, O, Biasin, E, Niebling, S, Petersson, J, Hoernke, M, Björling, A, Gustavsson, E, van Driel, TB, Dohn, AO, Laursen, M, Zederkof, DB, Tono, K, Katayama, T, Owada, S, Nielsen, MM, Davidsson, J, Uhlig, J, Hub, JS, Haldrup, K & Westenhoff, S 2023, 'Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering', Journal of the American Chemical Society, vol. 145, no. 29, pp. 15754-15765. https://doi.org/10.1021/jacs.3c00484

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 et al.
In: Journal of the American Chemical Society, Vol. 145, No. 29, 26.07.2023, p. 15754-15765.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Solvent-Dependent Structural Dynamics in the Ultrafast Photodissociation Reaction of Triiodide Observed with Time-Resolved X-ray Solution Scattering

AU - Nimmrich, Amke

AU - Panman, Matthijs R.

AU - Berntsson, Oskar

AU - Biasin, Elisa

AU - Niebling, Stephan

AU - Petersson, Jonas

AU - Hoernke, Maria

AU - Björling, Alexander

AU - Gustavsson, Emil

AU - van Driel, Tim B.

AU - Dohn, Asmus O.

AU - Laursen, Mads

AU - Zederkof, Diana B.

AU - Tono, Kensuke

AU - Katayama, Tetsuo

AU - Owada, Shigeki

AU - Nielsen, Martin M.

AU - Davidsson, Jan

AU - Uhlig, Jens

AU - Hub, Jochen S.

AU - Haldrup, Kristoffer

AU - Westenhoff, Sebastian

PY - 2023/7/26

Y1 - 2023/7/26

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85160799905

U2 - 10.1021/jacs.3c00484

DO - 10.1021/jacs.3c00484

M3 - Article

C2 - 37163700

AN - SCOPUS:85160799905

SN - 0002-7863

VL - 145

SP - 15754

EP - 15765

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 29

ER -

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

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