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

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.
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  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:
OSTI Identifier:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Nature Publishing Group
Research Org:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY chemical sciences; catalysis; condensed matter