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Title: Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

Abstract

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [1];  [4];  [4];  [8];  [8];  [9];  [4];  [1];  [1];  [4];  [10];  [5];  [10] more »;  [5];  [11];  [1];  [12];  [12];  [1];  [1];  [1]; ORCiD logo [11];  [1];  [1];  [4] « less
  1. Lund Univ., Lund (Sweden)
  2. Univ. of Copenhagen, Copenhagen (Denmark); Technical Univ. of Denmark, Lyngby (Denmark)
  3. Hungarian Academy Sciences, Budapest (Hungary)
  4. Technical Univ. of Denmark, Lyngby (Denmark)
  5. High Energy Accelerator Research Organization, Ibaraki (Japan)
  6. Hungarian Academy Sciences, Budapest (Hungary); Univ. Paris-Sud, Orsay Cedex (France)
  7. European XFEL, Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany)
  8. European XFEL, Hamburg (Germany)
  9. Argonne National Lab. (ANL), Argonne, IL (United States)
  10. Hungarian Academy of Sciences, Budapest (Hungary)
  11. RIKEN, Hyogo (Japan)
  12. Japan Synchrotron Radiation Research Institute, Hyogo (Japan)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1225221
Alternate Identifier(s):
OSTI ID: 1392021
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical sciences; catalysis; condensed matter

Citation Formats

Canton, Sophie E., Kjær, Kasper S., Vankó, György, van Driel, Tim B., Adachi, Shin -ichi, Bordage, Amélie, Bressler, Christian, Chabera, Pavel, Christensen, Morten, Dohn, Asmus O., Galler, Andreas, Gawelda, Wojciech, Gosztola, David, Haldrup, Kristoffer, Harlang, Tobias, Liu, Yizhu, Møller, Klaus B., Németh, Zoltán, Nozawa, Shunsuke, Pápai, Mátyás, Sato, Tokushi, Sato, Takahiro, Suarez-Alcantara, Karina, Togashi, Tadashi, Tono, Kensuke, Uhlig, Jens, Vithanage, Dimali A., Wärnmark, Kenneth, Yabashi, Makina, Zhang, Jianxin, Sundström, Villy, and Nielsen, Martin M.. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses. United States: N. p., 2015. Web. doi:10.1038/ncomms7359.
Canton, Sophie E., Kjær, Kasper S., Vankó, György, van Driel, Tim B., Adachi, Shin -ichi, Bordage, Amélie, Bressler, Christian, Chabera, Pavel, Christensen, Morten, Dohn, Asmus O., Galler, Andreas, Gawelda, Wojciech, Gosztola, David, Haldrup, Kristoffer, Harlang, Tobias, Liu, Yizhu, Møller, Klaus B., Németh, Zoltán, Nozawa, Shunsuke, Pápai, Mátyás, Sato, Tokushi, Sato, Takahiro, Suarez-Alcantara, Karina, Togashi, Tadashi, Tono, Kensuke, Uhlig, Jens, Vithanage, Dimali A., Wärnmark, Kenneth, Yabashi, Makina, Zhang, Jianxin, Sundström, Villy, & Nielsen, Martin M.. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses. United States. doi:10.1038/ncomms7359.
Canton, Sophie E., Kjær, Kasper S., Vankó, György, van Driel, Tim B., Adachi, Shin -ichi, Bordage, Amélie, Bressler, Christian, Chabera, Pavel, Christensen, Morten, Dohn, Asmus O., Galler, Andreas, Gawelda, Wojciech, Gosztola, David, Haldrup, Kristoffer, Harlang, Tobias, Liu, Yizhu, Møller, Klaus B., Németh, Zoltán, Nozawa, Shunsuke, Pápai, Mátyás, Sato, Tokushi, Sato, Takahiro, Suarez-Alcantara, Karina, Togashi, Tadashi, Tono, Kensuke, Uhlig, Jens, Vithanage, Dimali A., Wärnmark, Kenneth, Yabashi, Makina, Zhang, Jianxin, Sundström, Villy, and Nielsen, Martin M.. Mon . "Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses". United States. doi:10.1038/ncomms7359. https://www.osti.gov/servlets/purl/1225221.
@article{osti_1225221,
title = {Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses},
author = {Canton, Sophie E. and Kjær, Kasper S. and Vankó, György and van Driel, Tim B. and Adachi, Shin -ichi and Bordage, Amélie and Bressler, Christian and Chabera, Pavel and Christensen, Morten and Dohn, Asmus O. and Galler, Andreas and Gawelda, Wojciech and Gosztola, David and Haldrup, Kristoffer and Harlang, Tobias and Liu, Yizhu and Møller, Klaus B. and Németh, Zoltán and Nozawa, Shunsuke and Pápai, Mátyás and Sato, Tokushi and Sato, Takahiro and Suarez-Alcantara, Karina and Togashi, Tadashi and Tono, Kensuke and Uhlig, Jens and Vithanage, Dimali A. and Wärnmark, Kenneth and Yabashi, Makina and Zhang, Jianxin and Sundström, Villy and Nielsen, Martin M.},
abstractNote = {Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.},
doi = {10.1038/ncomms7359},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {Mon Mar 02 00:00:00 EST 2015},
month = {Mon Mar 02 00:00:00 EST 2015}
}

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Works referenced in this record:

Photoinduced electron transfer in supramolecular systems for artificial photosynthesis
journal, May 1992

  • Wasielewski, Michael R.
  • Chemical Reviews, Vol. 92, Issue 3, p. 435-461
  • DOI: 10.1021/cr00011a005

Femtosecond Clocking of the Chemical Bond
journal, September 1988