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

K Wiesner, A Naves de Brito, SL Sorensen, N Kosugi, O Bjorneholm

Research output: Contribution to journalArticle (Academic Journal)peer-review

2 Citations (Scopus)

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.
Translated title of the contributionCore excitation in O-3 localized to one of two symmetry-equivalent chemical bonds: Molecular alignment through vibronic coupling
Original languageEnglish
Article numberArticle no. 154303
Pages (from-to)1 - 5
Number of pages5
JournalJournal of Chemical Physics
Volume122 (15)
DOIs
Publication statusPublished - Apr 2005

Bibliographical note

Publisher: American Institute of Physics, Cirfulation & Fulfillment Div

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