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 2Σ or a 2Π 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 |
|---|---|
| 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 |
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- Physical and Theoretical Chemistry
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Formulation of the double differential and other cross-sections for the ClHCl- photodetachment process. / Balint-Kurti, Gabriel G.; Schatz, George C.
In: Journal of the Chemical Society - Faraday Transactions, Vol. 93, No. 5, 07.03.1997, p. 755-764.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Formulation of the double differential and other cross-sections for the ClHCl- photodetachment process
AU - Balint-Kurti, Gabriel G.
AU - Schatz, George C
PY - 1997/3/7
Y1 - 1997/3/7
N2 - 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 2Σ or a 2Π 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.
AB - 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 2Σ or a 2Π 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.
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M3 - Article
VL - 93
SP - 755
EP - 764
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 5
ER -