Photodetachment anisotropy for mixed s-p states: 8/3 and other fractions

Andrei M Sanov, Emily R. Grumbling, Daniel J. Goebbert, Lori M. Culberson

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

An approximate model for analytical prediction of photoelectron angular distributions in anion photodetachment from mixed s-p states is presented. Considering the dipole-allowed s, p, and d free-electron partial waves, the model describes photodetachment anisotropy in terms of the fractional p character of the initial orbital and the A and B coefficients describing the relative intensities of the p → d to p → s and s → p to p → s channels, respectively. The model represents an extension of the central-potential model to an intermediate regime encompassing varying degrees of s and p contributions to the initial bound orbital. This description is applicable to a broad class of hybrid molecular orbitals, particularly those localized predominantly on a single atom. Under the additional assumption of hydrogenic or Slater-type orbitals, the B/A ratio in photodetachment from a mixed 2s-2p state is shown to equal 8/3. Corresponding fractions are derived for other ns-np mixing cases. The predictions of the model are tested on several anion systems, including NH2- and CCl2 -. The quantitative discrepancies in the latter case are attributed to the breakdown of the central-atom approximation and a mechanism for corresponding corrections is indicated.

Original languageEnglish (US)
Article number054311
JournalThe Journal of Chemical Physics
Volume138
Issue number5
DOIs
StatePublished - Feb 7 2013

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photodetachment
Anisotropy
anisotropy
orbitals
Anions
anions
Atoms
Angular distribution
Molecular orbitals
Photoelectrons
predictions
free electrons
atoms
molecular orbitals
photoelectrons
angular distribution
breakdown
dipoles
Electrons
coefficients

ASJC Scopus subject areas

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

Cite this

Photodetachment anisotropy for mixed s-p states : 8/3 and other fractions. / Sanov, Andrei M; Grumbling, Emily R.; Goebbert, Daniel J.; Culberson, Lori M.

In: The Journal of Chemical Physics, Vol. 138, No. 5, 054311, 07.02.2013.

Research output: Contribution to journalArticle

Sanov, Andrei M ; Grumbling, Emily R. ; Goebbert, Daniel J. ; Culberson, Lori M. / Photodetachment anisotropy for mixed s-p states : 8/3 and other fractions. In: The Journal of Chemical Physics. 2013 ; Vol. 138, No. 5.
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