### Abstract

The theory of dissociative photodetachment of closed-shell linear triatomic molecular ions is developed with emphasis on ClHCl^{-}. The electronic states are described using a valence bond method, and the detachment process is assumed to be direct, and to produce a scattered electron in either an s or d type continuum orbital. The neutral ClHCl is assumed to be produced in either a ^{2}Σ or a ^{2}Π state, and its dissociation dynamics includes full coupling between electronic, vibrational, rotational and fine-structure states, and the possibility of dissociation into more than one product arrangement. A completely general expression for the electronic transition moment is used, and Franck-Condon approximations are not invoked. Simplifications to the rigorous expression for the double differential cross-section for dissociative photodetachment are considered, leading to an expression for the degeneracy averaged integral cross-section (summed over all magnetic quantum numbers) that is amenable to explicit evaluation based on wavefunctions from reactive scattering calculations.

Original language | English |
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Pages (from-to) | 755-764 |

Number of pages | 10 |

Journal | Journal of the Chemical Society - Faraday Transactions |

Volume | 93 |

Issue number | 5 |

Publication status | Published - Mar 7 1997 |

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

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## Cite this

^{-}photodetachment process.

*Journal of the Chemical Society - Faraday Transactions*,

*93*(5), 755-764.