Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [3];  [3];  [4];  [5];  [6];  [6];  [1];  [7];  [6];  [8];  [2]
  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
+ Show Author Affiliations

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.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Oulu (Finland)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Academy of Finland
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1429065
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 5 Vol. 9; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (55)

Libcint: An efficient general integral library for Gaussian basis functions journal June 2015
General atomic and molecular electronic structure system journal November 1993
Photoionization and ionic dissociation of the C 3 H 3 NS molecule induced by soft X-ray near the C1s edge journal August 2017
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
  • Defonsi Lestard, María Eliana; Tuttolomondo, María Eugenia; Wann, Derek A.
  • Journal of Raman Spectroscopy, Vol. 41, Issue 10 https://doi.org/10.1002/jrs.2550
journal November 2009
Use of bond orders and valences for the description and prediction of primary fragmentation processes journal November 1991
The influence of polarization functions on molecular orbital hydrogenation energies journal January 1973
Charge, bond order and valence in the AB initio SCF theory journal May 1983
Theoretical autoionization spectra of excited N2 and N2O journal December 1995
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
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
Homonuclear site-specific photochemistry by an ion–electron multi-coincidence spectroscopy technique journal October 2012
Auger electron–ion coincidence studies to probe molecular dynamics journal December 2004
Molecular fragmentation of pyrimidine derivatives following site-selective carbon core ionization journal April 2011
The ESCA molecule—Historical remarks and new results journal September 2012
Photofragmentation of Serine Following C 1s Core Ionization—Comparison with Cysteine journal July 2016
Site-Specific Electron-Relaxation Caused by Si:2p Core-Level Photoionization: Comparison between F 3 SiCH 2 CH 2 Si(CH 3 ) 3 and Cl 3 SiCH 2 CH 2 Si(CH 3 ) 3 Vapors by Means of Photoelectron Auger Electron Coincidence Spectroscopy journal December 2016
Multicoincidence mass spectrometry applied to hexamethyldisilane excited around the silicon 2p edge journal May 1993
A Study To Control Chemical Reactions Using Si:2p Core Ionization: Site-Specific Fragmentation journal August 2011
Fragmentation Dynamics of Doubly Charged Methionine in the Gas Phase journal February 2014
On Routes to Ultrafast Dissociation of Polyatomic Molecules journal June 2013
Femtosecond response of polyatomic molecules to ultra-intense hard X-rays journal May 2017
Hetero-site-specific X-ray pump-probe spectroscopy for femtosecond intramolecular dynamics journal May 2016
Site- and state-selected photofragmentation of 2Br-pyrimidine journal January 2015
Investigation of the fragmentation of core-ionised deoxyribose: a study as a function of the tautomeric form journal January 2015
Relative extent of double and single Auger decay in molecules containing C, N and O atoms journal January 2016
Femtosecond charge and molecular dynamics of I-containing organic molecules induced by intense X-ray free-electron laser pulses journal January 2016
New high luminosity “double toroidal” electron spectrometer journal October 1997
Development of a four-element conical electron lens dedicated to high resolution Auger electron–ion(s) coincidence experiments journal November 2002
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
Influence of formation path on the CH2BrCl2+ dissociation dynamics journal August 2005
Fragmentation patterns of doubly charged acrylonitrile molecule following carbon core ionization journal September 2009
Site‐selective fragmentation in core‐excited bromo‐chloro‐alkanes [Br(CH 2 ) n Cl] journal September 1994
A local chemical environment effect in site-specific Auger spectra of ethyl trifluoroacetate journal January 2013
Design of a lens table for a double toroidal electron spectrometer journal March 2013
Communication: Two-step explosion processes of highly charged fullerene cations C 60 q + ( q = 20–60) journal September 2014
Efficient electronic structure calculation for molecular ionization dynamics at high x-ray intensity journal May 2015
Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal) journal September 2016
CXII. On the analysis of τ-meson data and the nature of the τ-meson journal October 1953
EPICEA: Probing High-Energy Electron Emission In The Molecular Frame journal April 2014
Electron-ion-ion triple-coincidence spectroscopic study of site-specific fragmentation caused by Si : 2 p core-level photoionization of F 3 SiCH 2 CH 2 Si ( CH 3 ) 3 vapor journal February 2007
Impact of hollow-atom formation on coherent x-ray scattering at high intensity journal March 2011
Internal energy dependence in x-ray-induced molecular fragmentation: An experimental and theoretical study of thiophene journal April 2015
Ionization-site effects on the photofragmentation of chloro- and bromoacetic acid molecules journal December 2015
X-ray multiphoton ionization dynamics of a water molecule irradiated by an x-ray free-electron laser pulse journal August 2016
Ultrafast Charge Rearrangement and Nuclear Dynamics upon Inner-Shell Multiple Ionization of Small Polyatomic Molecules journal January 2013
Ultrafast Charge Transfer of a Valence Double Hole in Glycine Driven Exclusively by Nuclear Motion journal October 2015
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-Selective Photochemistry of Core Excited Molecules: Role of the Internal Energy journal November 1998
Ultrafast Dynamics of a Nucleobase Analogue Illuminated by a Short Intense X-ray Free Electron Laser Pulse journal June 2016
Electron spectroscopy for atoms, molecules, and condensed matter journal July 1982
Dynamics of Fragmentation Reactions From Peak Shapes in Multiparticle Coincidence Experiments journal January 1991

Cited By (6)

Spectroscopic Signature of Chemical Bond Dissociation Revealed by Calculated Core-Electron Spectra text January 2019
Investigating core-excited states of nitrosyl chloride (ClNO) and their break-up dynamics following Auger decay journal October 2018
NEXAFS spectra and specific dissociation of oligo-peptide model molecules journal August 2019
X-ray linear and non-linear spectroscopy of the ESCA molecule journal September 2019
Molecular-bond breaking induced by interatomic decay processes journal November 2019
Ab Initio Molecular Dynamics Simulations to Interpret the Molecular Fragmentation Induced in Deoxyribose by Synchrotron Soft X-Rays journal December 2019

Figures / Tables (4)

Figure 1(p. 6)figure Figure 1
Figure 2(p. 7)figure Figure 2
Figure 3(p. 10)figure Figure 3
Figure 4(p. 12)figure Figure 4

Similar Records

Inner-shell excitation and ionic fragmentation of molecules
Technical Report · Mon Mar 31 23:00:00 EST 1997 · OSTI ID:603474
Carbon dioxide ion dissociations after inner shell excitation and ionization: The origin of site-specific effects
Journal Article · Wed May 14 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:22252881
Experimental and ab initio study of the photofragmentation of DNA and RNA sugars
Journal Article · Thu Sep 15 00:00:00 EDT 2011 · Physical Review. A · OSTI ID:22068738

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY