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Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy

Author

Listed:
  • D. Mayer

    (Institut für Physik und Astronomie, Universität Potsdam)

  • F. Lever

    (Institut für Physik und Astronomie, Universität Potsdam)

  • D. Picconi

    (Universität Potsdam)

  • J. Metje

    (Institut für Physik und Astronomie, Universität Potsdam)

  • S. Alisauskas

    (Deutsches Elektronen Synchrotron (DESY))

  • F. Calegari

    (Center for Free-Electron Laser Science (CFEL), Deutsches Elektronen Synchrotron (DESY)
    Universität Hamburg
    Universität Hamburg)

  • S. Düsterer

    (Deutsches Elektronen Synchrotron (DESY))

  • C. Ehlert

    (Heidelberg Institute for Theoretical Studies, HITS gGmbH)

  • R. Feifel

    (University of Gothenburg)

  • M. Niebuhr

    (Institut für Physik und Astronomie, Universität Potsdam)

  • B. Manschwetus

    (Deutsches Elektronen Synchrotron (DESY))

  • M. Kuhlmann

    (Deutsches Elektronen Synchrotron (DESY))

  • T. Mazza

    (European XFEL)

  • M. S. Robinson

    (Institut für Physik und Astronomie, Universität Potsdam
    Center for Free-Electron Laser Science (CFEL), Deutsches Elektronen Synchrotron (DESY)
    Universität Hamburg)

  • R. J. Squibb

    (University of Gothenburg)

  • A. Trabattoni

    (Center for Free-Electron Laser Science (CFEL), Deutsches Elektronen Synchrotron (DESY))

  • M. Wallner

    (University of Gothenburg)

  • P. Saalfrank

    (Universität Potsdam)

  • T. J. A. Wolf

    (Stanford PULSE Institute, SLAC National Accelerator Laboratory)

  • M. Gühr

    (Institut für Physik und Astronomie, Universität Potsdam)

Abstract

The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.

Suggested Citation

  • D. Mayer & F. Lever & D. Picconi & J. Metje & S. Alisauskas & F. Calegari & S. Düsterer & C. Ehlert & R. Feifel & M. Niebuhr & B. Manschwetus & M. Kuhlmann & T. Mazza & M. S. Robinson & R. J. Squibb &, 2022. "Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-021-27908-y
    DOI: 10.1038/s41467-021-27908-y
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