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Photoelectron Diffraction Imaging of a Molecular Breakup Using an X-Ray Free-Electron Laser

Gregor Kastirke1, Markus S. Schöffler1, Miriam Weller1, Jonas Rist1, Rebecca Boll2, Nils Anders1, Thomas M. Baumann2, Sebastian Eckart1, Benjamin Erk3 et al.

Alberto De Fanis2, Kilian Fehre1, Averell Gatton4, Sven Grundmann1, Patrik Grychtol2, Alexander Hartung1, Max Hofmann1, Markus Ilchen2,5, Christian Janke1, Max Kircher1, Maksim Kunitski1, Xiang Li6, Tommaso Mazza2, Niklas Melzer1, Jacobo Montano2, Valerija Music2,5, Giammarco Nalin1, Yevheniy Ovcharenko2, Andreas Pier1, Nils Rennhack2, Daniel E. Rivas2, Reinhard Dörner1, Daniel Rolles6, Artem Rudenko6, Philipp Schmidt2,5, Juliane Siebert1, Nico Strenger1, Daniel Trabert1, Isabel Vela-Perez1, Rene Wagner2, Thorsten Weber7, Joshua B. Williams8, Pawel Ziolkowski2, Lothar Ph. H. Schmidt1, Achim Czasch1, Florian Trinter3,9, Michael Meyer2, Kiyoshi Ueda10, Philipp V. Demekhin5,*, and Till Jahnke1,†

  • 1Institut für Kernphysik, Goethe-Universität, Max-von-Laue-Strasse 1, 60438 Frankfurt am Main, Germany
  • 2European XFEL GmbH, Holzkoppel 4, 22869 Schenefeld, Germany
  • 3Deutsches Elektronen-Synchrotron (DESY), Notkestrasse 85, 22607 Hamburg, Germany
  • 4SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
  • 5Institut für Physik und CINSaT, Universität Kassel, Heinrich-Plett-Strasse 40, 34132 Kassel, Germany
  • 6J. R. Macdonald Laboratory, Department of Physics, Kansas State University, Manhattan, Kansas 66506, USA
  • 7Lawrence Berkeley National Laboratory, Chemical Sciences and Ultrafast X-ray Science Laboratory, Berkeley, California 94720, USA
  • 8Department of Physics, University of Nevada, Reno, Nevada 89557, USA
  • 9Molecular Physics, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
  • 10Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan

  • *demekhin@physik.uni-kassel.de
  • †jahnke@atom.uni-frankfurt.de
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Phys. Rev. X 10, 021052 – Published 8 June, 2020

DOI: https://doi.org/10.1103/PhysRevX.10.021052

Abstract

A central motivation for the development of x-ray free-electron lasers has been the prospect of time-resolved single-molecule imaging with atomic resolution. Here, we show that x-ray photoelectron diffraction—where a photoelectron emitted after x-ray absorption illuminates the molecular structure from within—can be used to image the increase of the internuclear distance during the x-ray-induced fragmentation of an O2 molecule. By measuring the molecular-frame photoelectron emission patterns for a two-photon sequential K-shell ionization in coincidence with the fragment ions, and by sorting the data as a function of the measured kinetic energy release, we can resolve the elongation of the molecular bond by approximately 1.2 a.u. within the duration of the x-ray pulse. The experiment paves the road toward time-resolved pump-probe photoelectron diffraction imaging at high-repetition-rate x-ray free-electron lasers.

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Popular Summary

The ability to see structural changes in single molecules during a chemical reaction has long been a dream of physicists and chemists. One suggested approach is to use finely tuned x-ray lasers to unleash electrons that illuminate a molecule from within. Using just such a setup, we create a movie that records the breakup of an oxygen molecule.

We use intense light pulses from an x-ray free-electron laser to emit an electron from an oxygen molecule. This photoelectron can be thought of as a wave, thanks to the wave-particle duality of quantum physics. As the electron wave propagates away from its host atom, it illuminates the geometrical features of the molecule, much like a radar or sonar measurement images the topology of a terrain. With this technique, we are able to obtain electron diffraction patterns that effectively “see” the nuclei separate within the 25-fs duration of the x-ray pulse.

Our measurement is a first of its kind, finally demonstrating that this experimental scheme is viable, employing novel x-ray free-electron laser sources and multicoincidence particle detection. In particular, the results suggest that time-resolved imaging of molecular rearrangement during photoreactions will be possible in the near future.

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References (26)

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  26. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevX.10.021052 for molecular-frame photoelectron angular distributions of the second photoelectron (emitted during the O+/O+ Coulomb explosion). The movie shows a sweep through different kinetic energy releases in the range of 28  eV<KER<36  eV. The red line is a fit using Legendre polynomials up to l = 9. The internuclear distances R have been obtained using the simple Coulomb explosion model (see Appendix B). The ion which is triply charged in the final state is located on the right.

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Phys. Rev. X 10, 021052– Published 8 June, 2020
  • Received 5 November 2019
  • Revised 30 March 2020
  • Accepted 15 April 2020
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.

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