Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy

Kasper S. Kjær*, Tim B. Van Driel, Tobias C.B. Harlang, Kristjan Kunnus, Elisa Biasin, Kathryn Ledbetter, Robert W. Hartsock, Marco E. Reinhard, Sergey Koroidov, Lin Li, Mads G. Laursen, Frederik B. Hansen, Peter Vester, Morten Christensen, Kristoffer Haldrup, Martin M. Nielsen, Asmus O. Dohn, Mátyás I. Pápai, Klaus B. Møller, Pavel Chabera & 20 others Yizhu Liu, Hideyuki Tatsuno, Cornelia Timm, Martin Jarenmark, Jens Uhlig, Villy Sundstöm, Kenneth Wärnmark, Petter Persson, Zoltán Németh, Dorottya Sárosiné Szemes, Éva Bajnóczi, György Vankó, Roberto Alonso-Mori, James M. Glownia, Silke Nelson, Marcin Sikorski, Dimosthenis Sokaras, Sophie E. Canton, Henrik T. Lemke, Kelly J. Gaffney

*Corresponding author for this work

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Abstract

Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2′-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.

Original languageEnglish
JournalChemical Science
Volume10
Issue number22
Pages (from-to)5749-5760
Number of pages12
ISSN2041-6520
DOIs
Publication statusPublished - 2019

Cite this

Kjær, K. S., Van Driel, T. B., Harlang, T. C. B., Kunnus, K., Biasin, E., Ledbetter, K., ... Gaffney, K. J. (2019). Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy. Chemical Science, 10(22), 5749-5760. https://doi.org/10.1039/c8sc04023k
Kjær, Kasper S. ; Van Driel, Tim B. ; Harlang, Tobias C.B. ; Kunnus, Kristjan ; Biasin, Elisa ; Ledbetter, Kathryn ; Hartsock, Robert W. ; Reinhard, Marco E. ; Koroidov, Sergey ; Li, Lin ; Laursen, Mads G. ; Hansen, Frederik B. ; Vester, Peter ; Christensen, Morten ; Haldrup, Kristoffer ; Nielsen, Martin M. ; Dohn, Asmus O. ; Pápai, Mátyás I. ; Møller, Klaus B. ; Chabera, Pavel ; Liu, Yizhu ; Tatsuno, Hideyuki ; Timm, Cornelia ; Jarenmark, Martin ; Uhlig, Jens ; Sundstöm, Villy ; Wärnmark, Kenneth ; Persson, Petter ; Németh, Zoltán ; Szemes, Dorottya Sárosiné ; Bajnóczi, Éva ; Vankó, György ; Alonso-Mori, Roberto ; Glownia, James M. ; Nelson, Silke ; Sikorski, Marcin ; Sokaras, Dimosthenis ; Canton, Sophie E. ; Lemke, Henrik T. ; Gaffney, Kelly J. / Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy. In: Chemical Science. 2019 ; Vol. 10, No. 22. pp. 5749-5760.
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title = "Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy",
abstract = "Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2′-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.",
author = "Kj{\ae}r, {Kasper S.} and {Van Driel}, {Tim B.} and Harlang, {Tobias C.B.} and Kristjan Kunnus and Elisa Biasin and Kathryn Ledbetter and Hartsock, {Robert W.} and Reinhard, {Marco E.} and Sergey Koroidov and Lin Li and Laursen, {Mads G.} and Hansen, {Frederik B.} and Peter Vester and Morten Christensen and Kristoffer Haldrup and Nielsen, {Martin M.} and Dohn, {Asmus O.} and P{\'a}pai, {M{\'a}ty{\'a}s I.} and M{\o}ller, {Klaus B.} and Pavel Chabera and Yizhu Liu and Hideyuki Tatsuno and Cornelia Timm and Martin Jarenmark and Jens Uhlig and Villy Sundst{\"o}m and Kenneth W{\"a}rnmark and Petter Persson and Zolt{\'a}n N{\'e}meth and Szemes, {Dorottya S{\'a}rosin{\'e}} and {\'E}va Bajn{\'o}czi and Gy{\"o}rgy Vank{\'o} and Roberto Alonso-Mori and Glownia, {James M.} and Silke Nelson and Marcin Sikorski and Dimosthenis Sokaras and Canton, {Sophie E.} and Lemke, {Henrik T.} and Gaffney, {Kelly J.}",
year = "2019",
doi = "10.1039/c8sc04023k",
language = "English",
volume = "10",
pages = "5749--5760",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "22",

}

Kjær, KS, Van Driel, TB, Harlang, TCB, Kunnus, K, Biasin, E, Ledbetter, K, Hartsock, RW, Reinhard, ME, Koroidov, S, Li, L, Laursen, MG, Hansen, FB, Vester, P, Christensen, M, Haldrup, K, Nielsen, MM, Dohn, AO, Pápai, MI, Møller, KB, Chabera, P, Liu, Y, Tatsuno, H, Timm, C, Jarenmark, M, Uhlig, J, Sundstöm, V, Wärnmark, K, Persson, P, Németh, Z, Szemes, DS, Bajnóczi, É, Vankó, G, Alonso-Mori, R, Glownia, JM, Nelson, S, Sikorski, M, Sokaras, D, Canton, SE, Lemke, HT & Gaffney, KJ 2019, 'Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy', Chemical Science, vol. 10, no. 22, pp. 5749-5760. https://doi.org/10.1039/c8sc04023k

Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy. / Kjær, Kasper S.; Van Driel, Tim B.; Harlang, Tobias C.B.; Kunnus, Kristjan; Biasin, Elisa; Ledbetter, Kathryn; Hartsock, Robert W.; Reinhard, Marco E.; Koroidov, Sergey; Li, Lin; Laursen, Mads G.; Hansen, Frederik B.; Vester, Peter; Christensen, Morten; Haldrup, Kristoffer; Nielsen, Martin M.; Dohn, Asmus O.; Pápai, Mátyás I.; Møller, Klaus B.; Chabera, Pavel; Liu, Yizhu; Tatsuno, Hideyuki; Timm, Cornelia; Jarenmark, Martin; Uhlig, Jens; Sundstöm, Villy; Wärnmark, Kenneth; Persson, Petter; Németh, Zoltán; Szemes, Dorottya Sárosiné; Bajnóczi, Éva; Vankó, György; Alonso-Mori, Roberto; Glownia, James M.; Nelson, Silke; Sikorski, Marcin; Sokaras, Dimosthenis; Canton, Sophie E.; Lemke, Henrik T.; Gaffney, Kelly J.

In: Chemical Science, Vol. 10, No. 22, 2019, p. 5749-5760.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy

AU - Kjær, Kasper S.

AU - Van Driel, Tim B.

AU - Harlang, Tobias C.B.

AU - Kunnus, Kristjan

AU - Biasin, Elisa

AU - Ledbetter, Kathryn

AU - Hartsock, Robert W.

AU - Reinhard, Marco E.

AU - Koroidov, Sergey

AU - Li, Lin

AU - Laursen, Mads G.

AU - Hansen, Frederik B.

AU - Vester, Peter

AU - Christensen, Morten

AU - Haldrup, Kristoffer

AU - Nielsen, Martin M.

AU - Dohn, Asmus O.

AU - Pápai, Mátyás I.

AU - Møller, Klaus B.

AU - Chabera, Pavel

AU - Liu, Yizhu

AU - Tatsuno, Hideyuki

AU - Timm, Cornelia

AU - Jarenmark, Martin

AU - Uhlig, Jens

AU - Sundstöm, Villy

AU - Wärnmark, Kenneth

AU - Persson, Petter

AU - Németh, Zoltán

AU - Szemes, Dorottya Sárosiné

AU - Bajnóczi, Éva

AU - Vankó, György

AU - Alonso-Mori, Roberto

AU - Glownia, James M.

AU - Nelson, Silke

AU - Sikorski, Marcin

AU - Sokaras, Dimosthenis

AU - Canton, Sophie E.

AU - Lemke, Henrik T.

AU - Gaffney, Kelly J.

PY - 2019

Y1 - 2019

N2 - Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2′-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.

AB - Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2′-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.

U2 - 10.1039/c8sc04023k

DO - 10.1039/c8sc04023k

M3 - Journal article

VL - 10

SP - 5749

EP - 5760

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 22

ER -