Advanced

Site-Selective Participator Decay of Core-Excited Butadiene

Ristinmaa Sörensen, Stacey LU ; Osbourne, S. J.; Ausmees, A.; Kikas, A.; Correia, N.; Naves de Brito, A.; Persson, Petter LU and Lunell, S. (1996) In Journal of Chemical Physics 105. p.10719-10724
Abstract
The decay of core-excited electronic states in free 1,3 trans butadiene molecules has been studied using high-resolution synchrotron radiation and electron spectrometry. The core-level energy shift between the terminal and central carbon atoms is 0.64 eV making selective excitation of core electrons from these atoms possible. Resonant excitation to the au(*) valence state leads to autoionizing decay channels which proceed according to the atomic site in the molecule. The radiationless decay is localized, and certain molecular orbitals are excluded from the decay depending upon the site of the core hole. This phenomenon is confirmed by semiempirical INDO calculations based upon the equivalent core approximation. The vibrational structure of... (More)
The decay of core-excited electronic states in free 1,3 trans butadiene molecules has been studied using high-resolution synchrotron radiation and electron spectrometry. The core-level energy shift between the terminal and central carbon atoms is 0.64 eV making selective excitation of core electrons from these atoms possible. Resonant excitation to the au(*) valence state leads to autoionizing decay channels which proceed according to the atomic site in the molecule. The radiationless decay is localized, and certain molecular orbitals are excluded from the decay depending upon the site of the core hole. This phenomenon is confirmed by semiempirical INDO calculations based upon the equivalent core approximation. The vibrational structure of the resonances below the carbon K edge has been measured and fit to extract vibrational energies and intensities, chemical shifts, and the lifetimes of the centrally and terminally excited states. The C 1s spectrum is also measured with vibrational resolution and the energies of the normal vibrational modes are extracted. The bond lengths are derived by application of a linear coupling analysis. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
105
pages
10719 - 10724
publisher
American Institute of Physics
external identifiers
  • scopus:0030381095
ISSN
0021-9606
DOI
10.1063/1.472874
language
English
LU publication?
yes
id
db296c96-d6ad-4932-aab7-7f24e5a17580 (old id 1457953)
date added to LUP
2009-08-27 14:32:49
date last changed
2017-01-01 05:11:47
@article{db296c96-d6ad-4932-aab7-7f24e5a17580,
  abstract     = {The decay of core-excited electronic states in free 1,3 trans butadiene molecules has been studied using high-resolution synchrotron radiation and electron spectrometry. The core-level energy shift between the terminal and central carbon atoms is 0.64 eV making selective excitation of core electrons from these atoms possible. Resonant excitation to the au(*) valence state leads to autoionizing decay channels which proceed according to the atomic site in the molecule. The radiationless decay is localized, and certain molecular orbitals are excluded from the decay depending upon the site of the core hole. This phenomenon is confirmed by semiempirical INDO calculations based upon the equivalent core approximation. The vibrational structure of the resonances below the carbon K edge has been measured and fit to extract vibrational energies and intensities, chemical shifts, and the lifetimes of the centrally and terminally excited states. The C 1s spectrum is also measured with vibrational resolution and the energies of the normal vibrational modes are extracted. The bond lengths are derived by application of a linear coupling analysis.},
  author       = {Ristinmaa Sörensen, Stacey and Osbourne, S. J. and Ausmees, A. and Kikas, A. and Correia, N. and Naves de Brito, A. and Persson, Petter and Lunell, S.},
  issn         = {0021-9606},
  language     = {eng},
  pages        = {10719--10724},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Site-Selective Participator Decay of Core-Excited Butadiene},
  url          = {http://dx.doi.org/10.1063/1.472874},
  volume       = {105},
  year         = {1996},
}