Photoelectron angular distributions in photodetachment from polarised d-like states: the case of HO2

Christopher C. Blackstone, Adam A. Wallace, Andrei Sanov

Research output: Contribution to journalArticlepeer-review

Abstract

We present a photoelectron imaging study of the angular distributions in HO2 photodetachment. The transitions studied correspond to electron detachment from the a HOMO and a′ HOMO−1 of HO2, yielding the neutral hydroperoxy radical in the ground and first excited electronic states. The experimental results are analysed using the p-d variant of the general model for photodetachment from mixed-character states. In this model, the parent anion molecular orbitals or the corresponding Dyson orbitals are described as superpositions of atomic p and d functions placed at a chosen centre in the molecular frame. As photoelectron angular distributions are sensitive to the long-range scaling of the parent orbitals, modelling the experimental results yields insight into the asymptotic behaviour of anionic wavefunctions. In the model, the long-range behaviour of diffuse orbitals is parameterised using the effective charges defining the basis functions. These parameters do not correspond to physical charges in the anion, but describe the long-range scaling of the p and d components of the model function and, therefore, the parent anion orbital. The experimental and model results for HO2 are compared to NO and O2, shedding light on the effects of molecular symmetry and chemical bonding structures on the photoelectron angular distributions.

Original languageEnglish (US)
Article numbere1831636
JournalMolecular Physics
Volume119
Issue number1-2
DOIs
StatePublished - 2021

Keywords

  • Negative ions
  • hydroperoxide anion
  • hydroperoxy radical
  • mixed-character states
  • photoelectron angular distributions

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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