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 SF6, SF5Cl, and POCl3. 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.
Founded in 1887, the Zeitschrift für Physikalische Chemie covers the main developments in physical chemistry, placing with an emphasis on experimental research. It represents a combination ofdiscusses reaction kinetics and spectroscopy, surface research and electrochemistry, thermodynamics and the structure analysis of matter in its various conditions, among other topics.