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

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. In this paper, 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. Finally, 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.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [4];  [5];  [6];  [6];  [1]; ORCiD logo [7];  [6];  [8];  [2]
+ Show Author Affiliations
  1. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science; The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany)
  2. Lund Univ. (Sweden). Dept. of Physics
  3. Univ. of Oulu (Finland). Faculty of Science. Nano and Molecular Systems Research Unit
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Northwestern Univ., Evanston, IL (United States). Dept. of Physics
  6. National Center for Scientific Research (CNRS), Paris (France). Lab. of Physical Chemistry - Matter and Radiation (LCPMR)
  7. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science; The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany); Univ. of Hamburg (Germany). Dept. of Physics
  8. Univ. of Chicago, IL (United States). Dept. of Physics. James Franck Inst.; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Oulu (Finland)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Academy of Finland
OSTI Identifier:
1429065
Grant/Contract Number:  
AC02-06CH11357; 296338
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 5; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Inhester, Ludger, Oostenrijk, Bart, Patanen, Minna, Kokkonen, Esko, Southworth, Stephen H., Bostedt, Christoph, Travnikova, Oksana, Marchenko, Tatiana, Son, Sang-Kil, Santra, Robin, Simon, Marc, Young, Linda, and Sorensen, Stacey L. Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.7b03235.
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Inhester, Ludger, Oostenrijk, Bart, Patanen, Minna, Kokkonen, Esko, Southworth, Stephen H., Bostedt, Christoph, Travnikova, Oksana, Marchenko, Tatiana, Son, Sang-Kil, Santra, Robin, Simon, Marc, Young, Linda, & Sorensen, Stacey L. Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation. United States. https://doi.org/10.1021/acs.jpclett.7b03235
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Inhester, Ludger, Oostenrijk, Bart, Patanen, Minna, Kokkonen, Esko, Southworth, Stephen H., Bostedt, Christoph, Travnikova, Oksana, Marchenko, Tatiana, Son, Sang-Kil, Santra, Robin, Simon, Marc, Young, Linda, and Sorensen, Stacey L. Wed . "Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation". United States. https://doi.org/10.1021/acs.jpclett.7b03235. https://www.osti.gov/servlets/purl/1429065.
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@article{osti_1429065,
title = {Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation},
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.},
abstractNote = {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. In this paper, 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. Finally, 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.},
doi = {10.1021/acs.jpclett.7b03235},
journal = {Journal of Physical Chemistry Letters},
number = 5,
volume = 9,
place = {United States},
year = {Wed Feb 14 00:00:00 EST 2018},
month = {Wed Feb 14 00:00:00 EST 2018}
}
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.7b03235
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Cited by: 29 works
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Figures / Tables:

Figure 1 Figure 1: Ion-mass spectra in coincidence with photoelectrons from different carbon ionization sites(CF3, CO2, CH2, CH3). Top left: the ion-mass spectra after site selection, based on the electron energy. Top right: The photoelectron spectrum showing the chemical shift of each photoelectron. The shaded areas indicate the selection range used inmore » the ion-mass spectra. Bottom: Branching ratios of fragment pairs containing a CFm+ (b) or CHn+ / C2Hn+ (c) fragment. The branching ratios are calculated from the measured abundance of double coincidence pairs that correspond to a photoelectron within the energy ranges shown in the top right.« less
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Works referenced in this record:

Ultrafast Charge Rearrangement and Nuclear Dynamics upon Inner-Shell Multiple Ionization of Small Polyatomic Molecules
journal, January 2013

On Routes to Ultrafast Dissociation of Polyatomic Molecules
journal, June 2013

  • Travnikova, Oksana; Kimberg, Victor; Flammini, Roberto
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 14
  • DOI: 10.1021/jz4011288

Ultrafast Charge Transfer of a Valence Double Hole in Glycine Driven Exclusively by Nuclear Motion
journal, October 2015

Hetero-site-specific X-ray pump-probe spectroscopy for femtosecond intramolecular dynamics
journal, May 2016

  • Picón, A.; Lehmann, C. S.; Bostedt, C.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11652

Ultrafast Dynamics of a Nucleobase Analogue Illuminated by a Short Intense X-ray Free Electron Laser Pulse
journal, June 2016

Femtosecond response of polyatomic molecules to ultra-intense hard X-rays
journal, May 2017

  • Rudenko, A.; Inhester, L.; Hanasaki, K.
  • Nature, Vol. 546, Issue 7656
  • DOI: 10.1038/nature22373

Subfemtosecond Control of Molecular Fragmentation by Hard X-Ray Photons
journal, May 2017

Site-Specific Fragmentation of Small Molecules Following Soft-X-Ray Excitation
journal, April 1983

Site- and state-selected photofragmentation of 2Br-pyrimidine
journal, January 2015

  • Bolognesi, P.; Kettunen, J. A.; Cartoni, A.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 37
  • DOI: 10.1039/C5CP02601F

Site‐selective fragmentation in core‐excited bromo‐chloro‐alkanes [Br(CH 2 ) n Cl]
journal, September 1994

  • Schmelz, H. C.; Reynaud, C.; Simon, M.
  • The Journal of Chemical Physics, Vol. 101, Issue 5
  • DOI: 10.1063/1.467558

Site-Selective Photochemistry of Core Excited Molecules: Role of the Internal Energy
journal, November 1998

Influence of formation path on the CH2BrCl2+ dissociation dynamics
journal, August 2005

  • Le Guen, K.; Ahmad, M.; Céolin, D.
  • The Journal of Chemical Physics, Vol. 123, Issue 8
  • DOI: 10.1063/1.2008256

Site-specific fragmentation caused by Si:1s core-level photoionization of F3SiCH2CH2Si(CH3)3 vapor
journal, September 2005

Site-specific fragmentation following F 1s photoionization of free CF3SF5 molecules studied by electron–ion coincidence spectroscopy
journal, November 2006

Site selective dissociation upon core ionization of ozone
journal, February 2007

  • Mocellin, Alexandra; Wiesner, Karoline; Sorensen, Stacey L.
  • Chemical Physics Letters, Vol. 435, Issue 4-6
  • DOI: 10.1016/j.cplett.2006.12.089

Fragmentation patterns of doubly charged acrylonitrile molecule following carbon core ionization
journal, September 2009

  • Itälä, E.; Kukk, E.; Ha, D. T.
  • The Journal of Chemical Physics, Vol. 131, Issue 11
  • DOI: 10.1063/1.3230107

Molecular fragmentation of pyrimidine derivatives following site-selective carbon core ionization
journal, April 2011

  • Itälä, E.; Ha, D. T.; Kooser, K.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 3-6
  • DOI: 10.1016/j.elspec.2011.01.007

A Study To Control Chemical Reactions Using Si:2p Core Ionization: Site-Specific Fragmentation
journal, August 2011

  • Nagaoka, Shin-ichi; Fukuzawa, Hironobu; Prümper, Georg
  • The Journal of Physical Chemistry A, Vol. 115, Issue 32
  • DOI: 10.1021/jp203664r

Homonuclear site-specific photochemistry by an ion–electron multi-coincidence spectroscopy technique
journal, October 2012

Fragmentation Dynamics of Doubly Charged Methionine in the Gas Phase
journal, February 2014

  • Ha, Dang Trinh; Wang, Y.; Alcamí, M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 8
  • DOI: 10.1021/jp4113238

Ionization-site effects on the photofragmentation of chloro- and bromoacetic acid molecules
journal, December 2015

Photofragmentation of Serine Following C 1s Core Ionization—Comparison with Cysteine
journal, July 2016

  • Itälä, Eero; Levola, Helena; Ha, Dang Trinh
  • The Journal of Physical Chemistry A, Vol. 120, Issue 28
  • DOI: 10.1021/acs.jpca.6b02554

Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal)
journal, September 2016

  • Zagorodskikh, Sergey; Eland, John H. D.; Zhaunerchyk, Vitali
  • The Journal of Chemical Physics, Vol. 145, Issue 12
  • DOI: 10.1063/1.4962823

Photoionization and ionic dissociation of the C 3 H 3 NS molecule induced by soft X-ray near the C1s edge
journal, August 2017

  • Lago, A. F.; Januário, R. D.; Cavasso Filho, R. L.
  • Journal of Mass Spectrometry, Vol. 52, Issue 10
  • DOI: 10.1002/jms.3968

Communication: Two-step explosion processes of highly charged fullerene cations C 60 q + ( q = 20–60)
journal, September 2014

  • Yamazaki, Kaoru; Nakamura, Takashi; Niitsu, Naoyuki
  • The Journal of Chemical Physics, Vol. 141, Issue 12
  • DOI: 10.1063/1.4896656

Investigation of the fragmentation of core-ionised deoxyribose: a study as a function of the tautomeric form
journal, January 2015

  • Hervé du Penhoat, Marie-Anne; Kamol Ghose, Krishna; Gaigeot, Marie-Pierre
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 48
  • DOI: 10.1039/C5CP05196G

A local chemical environment effect in site-specific Auger spectra of ethyl trifluoroacetate
journal, January 2013

  • Iwayama, H.; Sisourat, N.; Lablanquie, P.
  • The Journal of Chemical Physics, Vol. 138, Issue 2
  • DOI: 10.1063/1.4773294

Dynamics of Fragmentation Reactions From Peak Shapes in Multiparticle Coincidence Experiments
journal, January 1991

Multicoincidence mass spectrometry applied to hexamethyldisilane excited around the silicon 2p edge
journal, May 1993

  • Simon, M.; Lebrun, T.; Martins, R.
  • The Journal of Physical Chemistry, Vol. 97, Issue 20
  • DOI: 10.1021/j100122a011

CXII. On the analysis of τ-meson data and the nature of the τ-meson
journal, October 1953

  • Dalitz, R. H.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 44, Issue 357
  • DOI: 10.1080/14786441008520365

Use of bond orders and valences for the description and prediction of primary fragmentation processes
journal, November 1991

  • Somogyi, Árpád; Gömöry, Ágnes; Vékey, Károly
  • Organic Mass Spectrometry, Vol. 26, Issue 11
  • DOI: 10.1002/oms.1210261104

Predicting primary mass spectrometric cleavages: a `quasi-Koopmans' ab initio approach
journal, August 2001

Theoretical studies on the molecular dependence of the bond dissociation after the core excitations. CH3OCO(CH2)nCN, n=0, 1, 2
journal, October 2001

  • Takahashi, Osamu; Mitani, Masaki; Joyabu, Masanori
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 120, Issue 1-3
  • DOI: 10.1016/S0368-2048(01)00318-8

Relative extent of double and single Auger decay in molecules containing C, N and O atoms
journal, January 2016

  • Roos, A. Hult; Eland, J. H. D.; Andersson, J.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 36
  • DOI: 10.1039/C6CP02414A

New high luminosity “double toroidal” electron spectrometer
journal, October 1997

  • Miron, C.; Simon, M.; Leclercq, N.
  • Review of Scientific Instruments, Vol. 68, Issue 10
  • DOI: 10.1063/1.1148017

Development of a four-element conical electron lens dedicated to high resolution Auger electron–ion(s) coincidence experiments
journal, November 2002

  • Le Guen, K.; Céolin, D.; Guillemin, R.
  • Review of Scientific Instruments, Vol. 73, Issue 11
  • DOI: 10.1063/1.1511799

Auger electron–ion coincidence studies to probe molecular dynamics
journal, December 2004

  • Céolin, Denis; Miron, Catalin; Simon, Marc
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 141, Issue 2-3
  • DOI: 10.1016/j.elspec.2004.06.014

EPICEA: Probing High-Energy Electron Emission In The Molecular Frame
journal, April 2014

Design of a lens table for a double toroidal electron spectrometer
journal, March 2013

  • Liu, Xiao-Jing; Nicolas, Christophe; Miron, Catalin
  • Review of Scientific Instruments, Vol. 84, Issue 3
  • DOI: 10.1063/1.4794440

The ESCA molecule—Historical remarks and new results
journal, September 2012

  • Travnikova, Oksana; Børve, Knut J.; Patanen, Minna
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 185, Issue 8-9
  • DOI: 10.1016/j.elspec.2012.05.009

Experimental and theoretical structure and vibrational analysis of ethyl trifluoroacetate, CF 3 CO 2 CH 2 CH 3: Structure and vibrational analysis of CF 3 CO 2 CH 2 CH 3
journal, November 2009

  • Defonsi Lestard, María Eliana; Tuttolomondo, María Eugenia; Wann, Derek A.
  • Journal of Raman Spectroscopy, Vol. 41, Issue 10
  • DOI: 10.1002/jrs.2550

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

Efficient electronic structure calculation for molecular ionization dynamics at high x-ray intensity
journal, May 2015

  • Hao, Yajiang; Inhester, Ludger; Hanasaki, Kota
  • Structural Dynamics, Vol. 2, Issue 4
  • DOI: 10.1063/1.4919794

X-ray multiphoton ionization dynamics of a water molecule irradiated by an x-ray free-electron laser pulse
journal, August 2016

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527

The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973

  • Hariharan, P. C.; Pople, J. A.
  • Theoretica Chimica Acta, Vol. 28, Issue 3
  • DOI: 10.1007/BF00533485

Libcint: An efficient general integral library for Gaussian basis functions
journal, June 2015

  • Sun, Qiming
  • Journal of Computational Chemistry, Vol. 36, Issue 22
  • DOI: 10.1002/jcc.23981

Theoretical autoionization spectra of excited N2 and N2O
journal, December 1995

Impact of hollow-atom formation on coherent x-ray scattering at high intensity
journal, March 2011

Charge, bond order and valence in the AB initio SCF theory
journal, May 1983

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    • Inhester, Ludger; Li, Zheng; Zhu, Xiaolei
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