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

Kjær, Kasper S. LU ; Van Driel, Tim B.; Harlang, Tobias C.B. LU ; Kunnus, Kristjan; Biasin, Elisa; Ledbetter, Kathryn; Hartsock, Robert W.; Reinhard, Marco E.; Koroidov, Sergey and Li, Lin, et al. (2019) In Chemical Science 10(22). p.5749-5760
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... (More)

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.

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organization
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type
Contribution to journal
publication status
published
subject
in
Chemical Science
volume
10
issue
22
pages
12 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85067081804
ISSN
2041-6520
DOI
10.1039/c8sc04023k
language
English
LU publication?
yes
id
ddedc40d-d06a-4df8-9c8f-651253d7a8f7
date added to LUP
2019-07-02 15:12:51
date last changed
2019-08-11 04:51:17
@article{ddedc40d-d06a-4df8-9c8f-651253d7a8f7,
  abstract     = {<p>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)<sub>3</sub>]<sup>2+</sup>, 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.</p>},
  author       = {Kjær, Kasper S. and Van Driel, Tim B. and Harlang, Tobias C.B. and Kunnus, Kristjan and Biasin, Elisa and Ledbetter, Kathryn and Hartsock, Robert W. and Reinhard, Marco E. and Koroidov, Sergey and Li, Lin and Laursen, Mads G. and Hansen, Frederik B. and Vester, Peter and Christensen, Morten and Haldrup, Kristoffer and Nielsen, Martin M. and Dohn, Asmus O. and Pápai, Mátyás I. and Møller, Klaus B. and Chabera, Pavel and Liu, Yizhu and Tatsuno, Hideyuki and Timm, Cornelia and Jarenmark, Martin and Uhlig, Jens and Sundstöm, Villy and Wärnmark, Kenneth and Persson, Petter and Németh, Zoltán and Szemes, Dorottya Sárosiné and Bajnóczi, Éva and Vankó, György and Alonso-Mori, Roberto and Glownia, James M. and Nelson, Silke and Sikorski, Marcin and Sokaras, Dimosthenis and Canton, Sophie E. and Lemke, Henrik T. and Gaffney, Kelly J.},
  issn         = {2041-6520},
  language     = {eng},
  number       = {22},
  pages        = {5749--5760},
  publisher    = {Royal Society of Chemistry},
  series       = {Chemical Science},
  title        = {Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy},
  url          = {http://dx.doi.org/10.1039/c8sc04023k},
  volume       = {10},
  year         = {2019},
}