University of Oulu

Travnikova, O., Patanen, M., Söderström, J., Lindblad, A., Kas, J., Vila, F., Céolin, D., Marchenko, T., Goldsztejn, G., Guillemin, R., Journel, L., Carroll, T., Børve, K., Decleva, P., Rehr, J., Mårtensson, N., Simon, M., Svensson, S., Sæthre, L. (2019) Energy-Dependent Relative Cross Sections in Carbon 1s Photoionization: Separation of Direct Shake and Inelastic Scattering Effects in Single Molecules. J. Phys. Chem. A 2019, 123(35): 7619-7636.

Energy-dependent relative cross sections in carbon 1s photoionization : separation of direct shake and inelastic scattering effects in single molecules

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Author: Travnikova, Oksana1,2; Patanen, Minna3; Söderström, Johan4;
Organizations: 1LCPMR, CNRS, Sorbonne Université, UMR7614 Paris, France
2Synchrotron Soleil, L’Orme des Merisiers, Saint-Aubin, F-91192 Gif-sur-Yvette, France
3Nano and Molecular Systems Research Unit, Faculty of Science, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland
4Department of Physics and Astronomy, Uppsala University, P.O. Box 516, 75120 Uppsala, Sweden
5Department of Physics, University of Washington, Box 351560, Seattle, Washington 98195-1560, United States
6Division of Natural Sciences, Keuka College, Keuka Park, New York 14478, United States
7Department of Chemistry, University of Bergen, Allégaten 41, NO-5007 Bergen, Norway
8Dipartimento di Scienze Chimiche e Farmaceutiche, Universitá di Trieste and IOM-CNR, 34127 Trieste, Italy
Format: article
Version: accepted version
Access: open
Online Access: PDF Full Text (PDF, 2.7 MB)
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Language: English
Published: American Chemical Society, 2019
Publish Date: 2019-09-02


We demonstrate that the possibility of monitoring relative photoionization cross sections over a large photon energy range allows us to study and disentangle shake processes and intramolecular inelastic scattering effects. In this gas-phase study, relative intensities of the carbon 1s photoelectron lines from chemically inequivalent carbon atoms in the same molecule have been measured as a function of the incident photon energy in the range of 300–6000 eV. We present relative cross sections for the chemically shifted carbon 1s lines in the photoelectron spectra of ethyl trifluoroacetate (the “ESCA” molecule). The results are compared with those of methyl trifluoroacetate and S-ethyl trifluorothioacetate as well as a series of chloro-substituted ethanes and 2-butyne. In the soft X-ray energy range, the cross sections show an extended X-ray absorption fine structure type of wiggles, as was previously observed for a series of chloroethanes. The oscillations are damped in the hard X-ray energy range, but deviations of cross-section ratios from stoichiometry persist, even at high energies. The current findings are supported by theoretical calculations based on a multiple scattering model. The use of soft and tender X-rays provides a more complete picture of the dominant processes accompanying photoionization. Such processes reduce the main photoelectron line intensities by 20–60%. Using both energy ranges enabled us to discern the process of intramolecular inelastic scattering of the outgoing electron, whose significance is otherwise difficult to assess for isolated molecules. This effect relates to the notion of the inelastic mean free path commonly used in photoemission studies of clusters and condensed matter.

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Series: The journal of physical chemistry. A
ISSN: 1089-5639
ISSN-E: 1520-5215
ISSN-L: 1089-5639
Volume: 123
Issue: 35
Pages: 7619 - 7636
DOI: 10.1021/acs.jpca.9b05063
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: This work has been supported by the European Union Seventh Framework Programme FP7/2007-2013 under grant agreement no. 252781 (O.T.) and the ELISA (L.J.S., S.S.) and CALIPSO (L.J.S., K.J.B.) programs, by the Scientific Research Council (V.R.) in Sweden (S.S., N.M.), by the Norwegian high-performance computer consortium (NOTUR) through project number NN2506K (K.J.B., L.J.S.), by the I3 program (L.J.S., S.S.), by the Norwegian Research Council (K.J.B., L.S.), by the Academy of Finland (M.P.), by the Knut and Alice Wallenbergs Foundation (J.S.), by the U.S. Department of Energy Basic Energy Sciences grant no. DE-FG03-97ER45623 (J.J.R., J.J.K., and F.D.V.), by the Triangle de la Physique, France under contract no. 2007-010T (S.S.), and by the Agence Nationale de la Recherche, France under contract no. ANR-18-CE30-0015 (O.T.).
Dataset Reference: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.9b05063.
Copyright information: © 2019 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see