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Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation

Inhester, Ludger; Oostenrijk, Bart LU ; Patanen, Minna; Kokkonen, Esko LU ; Southworth, Stephen H.; Bostedt, Christoph; Travnikova, Oksana; Marchenko, Tatiana; Son, Sang Kil and Santra, Robin, et al. (2018) In Journal of Physical Chemistry Letters 9(5). p.1156-1163
Abstract

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... (More)

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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Journal of Physical Chemistry Letters
volume
9
issue
5
pages
8 pages
publisher
The American Chemical Society
external identifiers
  • scopus:85042687831
ISSN
1948-7185
DOI
10.1021/acs.jpclett.7b03235
language
English
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yes
id
f602c8e6-8aef-4ead-9042-0a1578ee53b3
date added to LUP
2018-03-16 15:13:18
date last changed
2018-11-21 21:38:40
@article{f602c8e6-8aef-4ead-9042-0a1578ee53b3,
  abstract     = {<p>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.</p>},
  author       = {Inhester, Ludger and Oostenrijk, Bart and Patanen, Minna and Kokkonen, Esko and Southworth, Stephen H. and Bostedt, Christoph and Travnikova, Oksana and Marchenko, Tatiana and Son, Sang Kil and Santra, Robin and Simon, Marc and Young, Linda and Sorensen, Stacey L.},
  issn         = {1948-7185},
  language     = {eng},
  month        = {03},
  number       = {5},
  pages        = {1156--1163},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry Letters},
  title        = {Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation},
  url          = {http://dx.doi.org/10.1021/acs.jpclett.7b03235},
  volume       = {9},
  year         = {2018},
}