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Exploring fingerprints of ultrafast structural dynamics in molecular solutions with an X-ray laser

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d3cp01257c· OSTI ID:2000049
 [1];  [2];  [3];  [4];  [2];  [5];  [6];  [7];  [8];  [2];  [9];  [10];  [11];  [12];  [9];  [13];  [9];  [6];  [9]
  1. European XFEL, Schenefeld (Germany); SLAC
  2. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  3. Technical University of Denmark, Lyngby (Denmark); University of Iceland, Reykjavík (Iceland)
  4. European XFEL, Schenefeld (Germany)
  5. University of California San Diego, La Jolla, CA (United States); University of Tübingen (Germany)
  6. Deutsches Elektronen-Synchrotron DESY, Hamburg (Germany)
  7. Deutsches Elektronen-Synchrotron DESY, Hamburg (Germany); University of Tübingen (Germany
  8. Technical University of Denmark, Lyngby (Denmark); European XFEL, Schenefeld (Germany)
  9. Technical University of Denmark, Lyngby (Denmark)
  10. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford University, CA (United States)
  11. University of California, Davis, CA (United States)
  12. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford University, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  13. Deutsches Elektronen-Synchrotron DESY, Hamburg (Germany); European XFEL, Schenefeld (Germany)
We apply ultrashort x-ray laser pulses to track optically excited structural dynamics of [Ir2(dimen)4]2+ molecules in solution. In our exploratory study we determine angular correlations in the scattered x-rays, which comprise a complex fingerprint of the ultrafast dynamics. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles. We unambiguously identify that in our experiment the photoinduced transition dipole moments in [Ir2(dimen)4]2+ molecules are oriented perpendicular to the Ir-Ir bond. The analysis also shows that the ground state conformer of [Ir2(dimen)4]2+ with a larger Ir–Ir distance is mostly responsible for the formation of the excited state. We also reveal that the ensemble of solute molecules can be characterized with a substantial structural heterogeneity due to solvent influence. In conclusion, the proposed x-ray correlation approach offers an alternative path for studies of ultrafast structural dynamics of molecular ensembles in the liquid and gas phases.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
Icelandic Research Fund (IRF); Independent Research Fund Denmark; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
2000049
Alternate ID(s):
OSTI ID: 1992169
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 35 Vol. 25; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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