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Title: Core localization and {sigma}* delocalization in the O 1s core-excited sulfur dioxide molecule

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{sub 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.

Authors:
; ;  [1];  [2];  [3];  [4];  [5]
  1. Department of Synchrotron Radiation Research, Institute of Physics, University of Lund, S-221 00 Lund (Sweden)
  2. UVSOR, Institute for Molecular Science (IMS), Myodaiji, Okazaki 444-8585 (Japan)
  3. MAX-Lab, Box 118, University of Lund, S-221 00 Lund (Sweden)
  4. Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden)
  5. Laboratorio Nacional de Luz Sincrotron (LNLS), Box 6192, 13084-971 Campinas SP (Brazil)
Publication Date:
OSTI Identifier:
21104006
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 128; Journal Issue: 11; Other Information: DOI: 10.1063/1.2844808; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CONFIGURATION INTERACTION; DIPOLE MOMENTS; DISSOCIATION; ELECTRONS; EXCITED STATES; GROUND STATES; HOLES; IONIZATION; IONS; MOLECULAR STRUCTURE; PHOTOLYSIS; SULFUR DIOXIDE; SYMMETRY BREAKING

Citation Formats

Lindgren, Andreas, Kivimaeki, Antti, Sorensen, Stacey L., Kosugi, Nobuhiro, Gisselbrecht, Mathieu, Burmeister, Florian, and Naves de Brito, Arnaldo. Core localization and {sigma}* delocalization in the O 1s core-excited sulfur dioxide molecule. United States: N. p., 2008. Web. doi:10.1063/1.2844808.
Lindgren, Andreas, Kivimaeki, Antti, Sorensen, Stacey L., Kosugi, Nobuhiro, Gisselbrecht, Mathieu, Burmeister, Florian, & Naves de Brito, Arnaldo. Core localization and {sigma}* delocalization in the O 1s core-excited sulfur dioxide molecule. United States. doi:10.1063/1.2844808.
Lindgren, Andreas, Kivimaeki, Antti, Sorensen, Stacey L., Kosugi, Nobuhiro, Gisselbrecht, Mathieu, Burmeister, Florian, and Naves de Brito, Arnaldo. Fri . "Core localization and {sigma}* delocalization in the O 1s core-excited sulfur dioxide molecule". United States. doi:10.1063/1.2844808.
@article{osti_21104006,
title = {Core localization and {sigma}* delocalization in the O 1s core-excited sulfur dioxide molecule},
author = {Lindgren, Andreas and Kivimaeki, Antti and Sorensen, Stacey L. and Kosugi, Nobuhiro and Gisselbrecht, Mathieu and Burmeister, Florian and Naves de Brito, Arnaldo},
abstractNote = {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{sub 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.},
doi = {10.1063/1.2844808},
journal = {Journal of Chemical Physics},
number = 11,
volume = 128,
place = {United States},
year = {Fri Mar 21 00:00:00 EDT 2008},
month = {Fri Mar 21 00:00:00 EDT 2008}
}