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  Low-energy constraints on photoelectron spectra measured from liquid water and aqueous solutions

Malerz, S., Trinter, F., Hergenhahn, U., Ghrist, A., Ali, H., Nicolas, C., et al. (2021). Low-energy constraints on photoelectron spectra measured from liquid water and aqueous solutions. Physical Chemistry Chemical Physics, 23(14), 8246-8260. doi:10.1039/D1CP00430A.

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 Creators:
Malerz, Sebastian1, Author           
Trinter, Florian1, 2, Author           
Hergenhahn, Uwe1, 3, Author           
Ghrist, Aaron1, 4, Author
Ali, Hebatallah1, 5, Author           
Nicolas, Christophe6, Author
Saak, Clara-Magdalena7, Author
Richter, Clemens1, 3, Author           
Hartweg, Sebastian6, Author
Nahon, Laurent6, Author
Lee, Chin1, 8, 9, Author           
Goy, Claudia10, Author
Neumark, Daniel M.8, 9, Author
Meijer, Gerard1, Author           
Wilkinson, Iain11, Author
Winter, Bernd1, Author           
Thürmer, Stephan12, Author
Affiliations:
1Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
2Institut für Kernphysik, Goethe-Universität, Max-von-Laue-Straβe, 60438 Frankfurt am Main, Germany, ou_persistent22              
3Leibniz Institute of Surface Engineering (IOM), Department of Functional Surfaces, 04318 Leipzig, Germany, ou_persistent22              
4Department of Chemistry, University of Southern California, Los Angeles, CA 90089, USA, ou_persistent22              
5Physics Department, Women Faculty for Art, Science and Education, Ain Shams University, Heliopolis, 11757 Cairo, Egypt, ou_persistent22              
6Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette, France, ou_persistent22              
7Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden, ou_persistent22              
8Department of Chemistry, University of California, Berkeley, CA 94720, USA, ou_persistent22              
9Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA , ou_persistent22              
10Centre for Molecular Water Science (CMWS), Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestraße 85, 22607 Hamburg, Germany, ou_persistent22              
11Department of Locally-Sensitive & Time-Resolved Spectroscopy, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin, Germany, ou_persistent22              
12Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-Ku, Kyoto 606-8502, Japan, ou_persistent22              

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 Abstract: We report on the effects of electron collision and indirect ionization processes, occurring at photoexcitation and electron kinetic energies well below 30 eV, on the photoemission spectra of liquid water. We show that the nascent photoelectron spectrum and, hence, the inferred electron binding energy can only be accurately determined if electron energies are large enough that cross sections for quasi-elastic scattering processes, such as vibrational excitation, are negligible. Otherwise, quasi-elastic scattering leads to strong, down-to-few-meV kinetic energy scattering losses from the direct photoelectron features, which manifest in severely distorted intrinsic photoelectron peak shapes. The associated cross-over point from predominant (known) electronically inelastic to quasi-elastic scattering seems to arise at surprisingly large electron kinetic energies, of approximately 10–14 eV. Concomitantly, we present evidence for the onset of indirect, autoionization phenomena (occurring via superexcited states) within a few eV of the primary and secondary ionization thresholds. These processes are inferred to compete with the direct ionization channels and primarily produce low-energy photoelectrons at photon and electron impact excitation energies below ∼15 eV. Our results highlight that vibrational inelastic electron scattering processes and neutral photoexcitation and autoionization channels become increasingly important when photon and electron kinetic energies are decreased towards the ionization threshold. Correspondingly, we show that for neat water and aqueous solutions, great care must be taken when quantitatively analyzing photoelectron spectra measured too close to the ionization threshold. Such care is essential for the accurate determination of solvent and solute ionization energies as well as photoelectron branching ratios and peak magnitudes.

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Language(s): eng - English
 Dates: 2021-01-292021-02-232021-02-242021-04-14
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/D1CP00430A
 Degree: -

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Project name : AQUACHIRAL - Chiral aqueous-phase chemistry
Grant ID : 883759
Funding program : Horizon 2020 (H2020)
Funding organization : European Commission (EC)

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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: 15 Volume / Issue: 23 (14) Sequence Number: - Start / End Page: 8246 - 8260 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1