University of Oulu

Inhester, L., Oostenrijk, B., Patanen, M., Kokkonen, E., Southworth, S., Bostedt, C., Travnikova, O., Marchenko, T., Son, S., Santra, R., Simon, M., Young, L., Sorensen, S. (2018) Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation. Journal of Physical Chemistry Letters, 9 (5), 1156-1163. doi:10.1021/acs.jpclett.7b03235

Chemical understanding of the limited site-specificity in molecular inner-shell photofragmentation

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Author: Inhester, Ludger1,2; Oostenrijk, Bart3; Patanen, Minna4;
Organizations: 1Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg, Germany
2The Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg, Germany
3Department of Physics, Lund University, Box 118, 221 00 Lund, Sweden
4Faculty of Science, Nano and Molecular Systems Research Unit, University of Oulu, Box 3000, FIN-90014 Oulu, Finland
5Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, Illinois 60439, United States
6Department of Physics, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
7Sorbonne Université, CNRS, Laboratoire de Chimie Physique - Matière et Rayonnement, LCPMR, F-75005 Paris, France
8Department of Physics, University of Hamburg, Jungiusstrasse 9, 20355 Hamburg, Germany
9Department of Physics and James Franck Institute, The University of Chicago, Chicago, Illinois 60637, United States
Format: article
Version: accepted version
Access: open
Online Access: PDF Full Text (PDF, 3.2 MB)
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Language: English
Published: American Chemical Society, 2018
Publish Date: 2019-02-14


In many cases fragmentation of molecules upon inner-shell ionization is very unspecific with respect to the initially localized ionization site. Often this finding is interpreted in terms of an equilibration of internal energy into vibrational degrees of freedom after Auger decay. We investigate the X-ray photofragmentation of ethyl trifluoroacetate upon core electron ionization at environmentally distinct carbon sites using photoelectron–photoion–photoion coincidence measurements and ab initio electronic structure calculations. For all four carbon ionization sites, the Auger decay weakens the same bonds and transfers the two charges to opposite ends of the molecule, which leads to a rapid dissociation into three fragments, followed by further fragmentation steps. The lack of site specificity is attributed to the character of the dicationic electronic states after Auger decay instead of a fast equilibration of internal energy.

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Series: Journal of physical chemistry letters
ISSN: 1948-7185
ISSN-E: 1948-7185
ISSN-L: 1948-7185
Volume: 9
Issue: 5
Pages: 1156 - 1163
DOI: 10.1021/acs.jpclett.7b03235
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: Work by M.P. was supported by Academy of Finland (decision no. 296338). Work by S.H.S., C.B., and L.Y. was supported by the U.S. Department of Energy, Office of Science, Basic Energy Science, Chemical Sciences, Geosciences and Biosciences Division under contract no. DE-AC02-06CH11357. We acknowledge SOLEIL for provision of synchrotron radiation facilities (Proposal No. 20160380) and we would like to thank A. Milosavljevic and C. Nicolas for assistance in using beamline PLEIADES.
Academy of Finland Grant Number: 296338
Detailed Information: 296338 (Academy of Finland Funding decision)
Dataset Reference: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpclett.7b03235.
Copyright information: © 2018 American Chemical Society