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Core localization and sigma( *) delocalization in the O 1s core-excited sulfur dioxide molecule.

Lindgren, Andreas LU ; Kosugi, Nobuhiro; Gisselbrecht, Mathieu LU ; Kivimäki, Antti; Burmeister, Florian; Naves de Brito, Arnaldo and Ristinmaa Sörensen, Stacey LU (2008) In Journal of Chemical Physics 128(11).
Abstract
Electron-ion-ion coincidence measurements of sulfur dioxide at discrete resonances near the O 1s ionization edge are reported. The spectra are analyzed using a model based upon molecular symmetry and on the geometry of the molecule. We find clear evidence for molecular alignment that can be ascribed to symmetry properties of the ground and core-excited states. Configuration interaction (CI) calculations indicate geometry changes in accord with the measured spectra. For the SO(2) molecule, however, we find that the localized core hole does not produce measurable evidence for valence localization, since the transition dipole moment is not parallel to a breaking sigma(*) O-S bond, in contrast to the case of ozone. The dissociation behavior... (More)
Electron-ion-ion coincidence measurements of sulfur dioxide at discrete resonances near the O 1s ionization edge are reported. The spectra are analyzed using a model based upon molecular symmetry and on the geometry of the molecule. We find clear evidence for molecular alignment that can be ascribed to symmetry properties of the ground and core-excited states. Configuration interaction (CI) calculations indicate geometry changes in accord with the measured spectra. For the SO(2) molecule, however, we find that the localized core hole does not produce measurable evidence for valence localization, since the transition dipole moment is not parallel to a breaking sigma(*) O-S bond, in contrast to the case of ozone. The dissociation behavior based upon the CI calculations using symmetry-broken orbitals while fixing a localized core-hole site is found to be nearly equivalent to that using symmetry-adapted orbitals. This implies that the core-localization effect is not strong enough to localize the sigma(*) valence orbital. (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
128
issue
11
publisher
American Institute of Physics
external identifiers
  • pmid:18361575
  • wos:000254292500031
  • scopus:41049105684
ISSN
0021-9606
DOI
10.1063/1.2844808
language
English
LU publication?
yes
id
148e34c5-0b5f-4faa-a4f3-ac2df9e4dab5 (old id 1052214)
date added to LUP
2008-04-03 12:44:42
date last changed
2017-01-01 05:05:22
@article{148e34c5-0b5f-4faa-a4f3-ac2df9e4dab5,
  abstract     = {Electron-ion-ion coincidence measurements of sulfur dioxide at discrete resonances near the O 1s ionization edge are reported. The spectra are analyzed using a model based upon molecular symmetry and on the geometry of the molecule. We find clear evidence for molecular alignment that can be ascribed to symmetry properties of the ground and core-excited states. Configuration interaction (CI) calculations indicate geometry changes in accord with the measured spectra. For the SO(2) molecule, however, we find that the localized core hole does not produce measurable evidence for valence localization, since the transition dipole moment is not parallel to a breaking sigma(*) O-S bond, in contrast to the case of ozone. The dissociation behavior based upon the CI calculations using symmetry-broken orbitals while fixing a localized core-hole site is found to be nearly equivalent to that using symmetry-adapted orbitals. This implies that the core-localization effect is not strong enough to localize the sigma(*) valence orbital.},
  articleno    = {114311},
  author       = {Lindgren, Andreas and Kosugi, Nobuhiro and Gisselbrecht, Mathieu and Kivimäki, Antti and Burmeister, Florian and Naves de Brito, Arnaldo and Ristinmaa Sörensen, Stacey},
  issn         = {0021-9606},
  language     = {eng},
  number       = {11},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Core localization and sigma( *) delocalization in the O 1s core-excited sulfur dioxide molecule.},
  url          = {http://dx.doi.org/10.1063/1.2844808},
  volume       = {128},
  year         = {2008},
}