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Core excitation in O-3 localized to one of two symmetry-equivalent chemical bonds: Molecular alignment through vibronic coupling

Wiesner, K; de Brito, A N; Ristinmaa Sörensen, Stacey LU ; Kosugi, N and Bjorneholm, O (2005) In Journal of Chemical Physics 122(15).
Abstract
Core excitation from terminal oxygen O-T in O-3 is shown to be an excitation from a localized core orbital to a localized valence orbital. The valence orbital is localized to one of the two equivalent chemical bonds. We experimentally demonstrate this with the Auger-Doppler effect which is observable when O-3 is core excited to the highly dissociative O(T)1S(-)17a(1)(1) state. Auger electrons emitted from the atomic oxygen fragment carry information about the molecular orientation relative to the electromagnetic-field vector at the moment of excitation. The data together with analytical functions for the electron-peak profiles give clear evidence that the preferred molecular orientation for excitation only depends on the orientation of one... (More)
Core excitation from terminal oxygen O-T in O-3 is shown to be an excitation from a localized core orbital to a localized valence orbital. The valence orbital is localized to one of the two equivalent chemical bonds. We experimentally demonstrate this with the Auger-Doppler effect which is observable when O-3 is core excited to the highly dissociative O(T)1S(-)17a(1)(1) state. Auger electrons emitted from the atomic oxygen fragment carry information about the molecular orientation relative to the electromagnetic-field vector at the moment of excitation. The data together with analytical functions for the electron-peak profiles give clear evidence that the preferred molecular orientation for excitation only depends on the orientation of one bond, not on the total molecular orientation. The localization of the valence orbital "7a(1)" is caused by mixing of the valence orbital "5b(2)" through vibronic coupling of antisymmetric stretching mode with b(2) symmetry. To the best of our knowledge, it is the first discussion of the localization of a core excitation of O-3. This result explains the success of the widely used assumption of localized core excitation in adsorbates and large molecules. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
122
issue
15
publisher
American Institute of Physics
external identifiers
  • wos:000229185400017
  • scopus:20844462841
ISSN
0021-9606
DOI
10.1063/1.1881192
language
English
LU publication?
yes
id
a0218e22-8cb9-435c-bf44-35915b8f58dd (old id 239033)
date added to LUP
2007-08-08 11:07:03
date last changed
2017-01-01 04:40:48
@article{a0218e22-8cb9-435c-bf44-35915b8f58dd,
  abstract     = {Core excitation from terminal oxygen O-T in O-3 is shown to be an excitation from a localized core orbital to a localized valence orbital. The valence orbital is localized to one of the two equivalent chemical bonds. We experimentally demonstrate this with the Auger-Doppler effect which is observable when O-3 is core excited to the highly dissociative O(T)1S(-)17a(1)(1) state. Auger electrons emitted from the atomic oxygen fragment carry information about the molecular orientation relative to the electromagnetic-field vector at the moment of excitation. The data together with analytical functions for the electron-peak profiles give clear evidence that the preferred molecular orientation for excitation only depends on the orientation of one bond, not on the total molecular orientation. The localization of the valence orbital "7a(1)" is caused by mixing of the valence orbital "5b(2)" through vibronic coupling of antisymmetric stretching mode with b(2) symmetry. To the best of our knowledge, it is the first discussion of the localization of a core excitation of O-3. This result explains the success of the widely used assumption of localized core excitation in adsorbates and large molecules.},
  articleno    = {154303},
  author       = {Wiesner, K and de Brito, A N and Ristinmaa Sörensen, Stacey and Kosugi, N and Bjorneholm, O},
  issn         = {0021-9606},
  language     = {eng},
  number       = {15},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Core excitation in O-3 localized to one of two symmetry-equivalent chemical bonds: Molecular alignment through vibronic coupling},
  url          = {http://dx.doi.org/10.1063/1.1881192},
  volume       = {122},
  year         = {2005},
}