On the Competition Between Electron Autodetachment and Dissociation of Molecular Anions

We treat the competition between autodetachment of electrons and unimolecular dissociation of excited molecular anions as a rigid-/loose-activated complex multichannel reaction system. To start, the temperature and pressure dependences under thermal excitation conditions are represented in terms of...

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Bibliographic Details
Published inJournal of the American Society for Mass Spectrometry Vol. 30; no. 10; p. 1828
Main Authors Marowsky, Gerd, Troe, Jürgen, Viggiano, Albert A
Format Journal Article
LanguageEnglish
Published United States 01.10.2019
Subjects
Anion dissociation
Electron autodetachment
Rotational channel switching
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Summary:We treat the competition between autodetachment of electrons and unimolecular dissociation of excited molecular anions as a rigid-/loose-activated complex multichannel reaction system. To start, the temperature and pressure dependences under thermal excitation conditions are represented in terms of falloff curves of separated single-channel processes within the framework of unimolecular reaction kinetics. Channel couplings, caused by collisional energy transfer and "rotational channel switching" due to angular momentum effects, are introduced afterward. The importance of angular momentum considerations is stressed in addition to the usual energy treatment. Non-thermal excitation conditions, such as typical for chemical activation and complex-forming bimolecular reactions, are considered as well. The dynamics of excited SF anions serves as the principal example. Other anions such as CF and POCl are also discussed.
ISSN:1879-1123