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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-triggeredmore » molecular systems involving 3d transition metals.« less

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [4];  [2];  [5]; ORCiD logo [2];  [2]; ORCiD logo [2];  [4];  [4];  [4]; ORCiD logo [4];  [4]; ORCiD logo [4]; ORCiD logo [6];  [7]; ORCiD logo [6]; ORCiD logo [8] more »;  [8];  [8];  [8];  [8];  [8];  [8];  [8]; ORCiD logo [8]; ORCiD logo [9]; ORCiD logo [9];  [9]; ORCiD logo [9];  [2];  [2];  [2];  [2];  [2]; ORCiD logo [10];  [11]; ORCiD logo [2] « less
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ. (Sweden)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ. (Sweden)
  4. Technical Univ. of Denmark, Lyngby (Denmark)
  5. PULSE Institute; SLAC National Accelerator Laboratory; Stanford University; Menlo Park; USA
  6. Univ. of Iceland, Reykjavik (Iceland)
  7. Univ. of Iceland, Reykjavik (Iceland); Hungarian Academy of Sciences, Budapest (Hungary)
  8. Lund Univ. (Sweden)
  9. Hungarian Academy of Sciences, Budapest (Hungary)
  10. ELI-ALPS, ELI-HU Non-Profit Ltd., Szeged (Hungary); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  11. SLAC National Accelerator Lab., Menlo Park, CA (United States); SwissFEL, Paul Scherrer Institut, Villigen PSI (Switzerland)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1512322
Alternate Identifier(s):
OSTI ID: 1546950
Grant/Contract Number:  
AC02-76SF00515; LP2013-59; VEKOP-2.3.2-16-2017-00015; ERC-StG-259709; K 109257; KAW 2014.0370; DFF-4002-00272B; DFF-8021-00347B
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 10; Journal Issue: 22; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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., and Gaffney, Kelly J. Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy. United States: N. p., 2019. Web. doi: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. United States. doi: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., and Gaffney, Kelly J. Mon . "Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy". United States. doi:10.1039/c8sc04023k.
@article{osti_1512322,
title = {Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy},
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.},
abstractNote = {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.},
doi = {10.1039/c8sc04023k},
journal = {Chemical Science},
number = 22,
volume = 10,
place = {United States},
year = {2019},
month = {4}
}

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DOI: 10.1039/c8sc04023k

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