Vibronic coupling in the superoxide anion

The vibrational dependence of the photoelectron angular distribution

Matthew Van Duzor, Foster Mbaiwa, Jie Wei, Tulsi Singh, Richard Mabbs, Andrei M Sanov, Steven J. Cavanagh, Stephen T. Gibson, Brenton R. Lewis, Jason R. Gascooke

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

We present a comprehensive photoelectron imaging study of theO 2(X2g, v′ =0-6) ←O 2- (X2Πg, v″ =0) and O 2 (a 1Δg, v′=0-4)←O 2-((X2Πg, v″ =0) photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v′ =1-4 data for detachment into the ground electronic state, presented in a recent communication [R. Mabbs, F. Mbaiwa, J. Wei, M. Van Duzor, S. T. Gibson, S. J. Cavanagh, and B. R. Lewis, Phys. Rev. A 82, 011401(R) (2010)]. Measured vibronic intensities are compared to Franck-Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model [R. M. Stehman and S. B. Woo, Phys. Rev. A 23, 2866 (1981)]. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy, β (E), displays the characteristics of photodetachment from a d -like orbital, consistent with the πg 2p highest occupied molecular orbital ofO2-. However, differences exist between the β trends for detachment into different vibrational levels of the X 2g and a 1Δg electronic states ofO2-. The ZCC model invokes vibrational channel specific "detachment orbitals" and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O2: the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models.

Original languageEnglish (US)
Article number174311
JournalThe Journal of Chemical Physics
Volume133
Issue number17
DOIs
StatePublished - Nov 7 2010

Fingerprint

Angular distribution
inorganic peroxides
Photoelectrons
detachment
Superoxides
photodetachment
photoelectrons
angular distribution
anions
Electronic states
orbitals
Anions
Electrons
electronics
electrons
Molecular orbitals
Binding energy
Kinetic energy
molecular orbitals
Anisotropy

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Vibronic coupling in the superoxide anion : The vibrational dependence of the photoelectron angular distribution. / Van Duzor, Matthew; Mbaiwa, Foster; Wei, Jie; Singh, Tulsi; Mabbs, Richard; Sanov, Andrei M; Cavanagh, Steven J.; Gibson, Stephen T.; Lewis, Brenton R.; Gascooke, Jason R.

In: The Journal of Chemical Physics, Vol. 133, No. 17, 174311, 07.11.2010.

Research output: Contribution to journalArticle

Van Duzor, M, Mbaiwa, F, Wei, J, Singh, T, Mabbs, R, Sanov, AM, Cavanagh, SJ, Gibson, ST, Lewis, BR & Gascooke, JR 2010, 'Vibronic coupling in the superoxide anion: The vibrational dependence of the photoelectron angular distribution', The Journal of Chemical Physics, vol. 133, no. 17, 174311. https://doi.org/10.1063/1.3493349
Van Duzor, Matthew ; Mbaiwa, Foster ; Wei, Jie ; Singh, Tulsi ; Mabbs, Richard ; Sanov, Andrei M ; Cavanagh, Steven J. ; Gibson, Stephen T. ; Lewis, Brenton R. ; Gascooke, Jason R. / Vibronic coupling in the superoxide anion : The vibrational dependence of the photoelectron angular distribution. In: The Journal of Chemical Physics. 2010 ; Vol. 133, No. 17.
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