### 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 NH_{2}^{-} and CCl_{2} ^{-}. 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 language | English (US) |
---|---|

Article number | 054311 |

Journal | The Journal of Chemical Physics |

Volume | 138 |

Issue number | 5 |

DOIs | |

State | Published - Feb 7 2013 |

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### ASJC Scopus subject areas

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

### Cite this

*The Journal of Chemical Physics*,

*138*(5), [054311]. https://doi.org/10.1063/1.4789811

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

Research output: Contribution to journal › Article

*The Journal of Chemical Physics*, vol. 138, no. 5, 054311. https://doi.org/10.1063/1.4789811

}

TY - JOUR

T1 - Photodetachment anisotropy for mixed s-p states

T2 - 8/3 and other fractions

AU - Sanov, Andrei M

AU - Grumbling, Emily R.

AU - Goebbert, Daniel J.

AU - Culberson, Lori M.

PY - 2013/2/7

Y1 - 2013/2/7

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84873615149&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84873615149&partnerID=8YFLogxK

U2 - 10.1063/1.4789811

DO - 10.1063/1.4789811

M3 - Article

C2 - 23406123

AN - SCOPUS:84873615149

VL - 138

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 5

M1 - 054311

ER -