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A localized view on molecular dissociation via electron-ion partial covariance

Journal Article · · Communications Chemistry
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  1. Univ. of Oxford (United Kingdom); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  2. Universität Kassel (Germany); European XFEL, Schenefeld (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  3. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science
  4. European XFEL, Schenefeld (Germany)
  5. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  6. Universität Kassel (Germany); European XFEL, Schenefeld (Germany)
  7. Univ. of Oxford (United Kingdom)
  8. Universität Kassel (Germany)
  9. Stockholm Univ. (Sweden)
  10. Univ. of Oxford (United Kingdom); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  11. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science; Peking Univ., Beijing (China)
  12. Max Born Institute, Berlin (Germany)
  13. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  14. Univ. of Gothenburg (Sweden)
  15. Kansas State Univ., Manhattan, KS (United States)

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); EPSRC Programme Grants; Deutsche Forschungsgemeinschaft (DFG); Max Planck Society; Volkswagon Foundation; Helmholtz Initiative; National Science Foundation (NSF)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1866598
Journal Information:
Communications Chemistry, Journal Name: Communications Chemistry Journal Issue: 1 Vol. 5; ISSN 2399-3669
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

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