On the Temperature Dependence of the Thermal Electron Attachment to SF6, SF5Cl, and POCl3

A simplified model for electron attachment to neutral molecules, separating electron--phonon coupling (or intramolecular vibrational redistribution, IVR) factors into an electronic and a vibrational contribution, is tested by comparison with experimental results for the nondissociative electron atta...

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Published inZeitschrift für physikalische Chemie (Neue Folge) Vol. 225; no. 11; pp. 1405 - 1416
Main Authors Troe, Hans-Jürgen, Marowsky, Gerd, Shuman, Nicholas S., Miller, Thomas M., Viggiano, Albert A.
Format Journal Article
LanguageEnglish
Published De Gruyter Oldenbourg 01.12.2011
Subjects
electron attachment
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Summary:A simplified model for electron attachment to neutral molecules, separating electron--phonon coupling (or intramolecular vibrational redistribution, IVR) factors into an electronic and a vibrational contribution, is tested by comparison with experimental results for the nondissociative electron attachments to SF , SF Cl, and POCl . It is shown that the experimental results can approximately be reproduced by the fit of two parameters, one of them characterizing the dependence of the IVR factor on the electron energy and one accounting for an effective threshold energy for overlap of vibrational wave functions on anionic and neutral potential energy surfaces. After fitting these parameters, temperature dependences over wide ranges of conditions can be represented. Likewise, kinetic modeling of dissociative processes of the highly excited anions produced by attachment is facilitated.
ISSN:0942-9352
2196-7156
DOI:10.1524/zpch.2011.0187