An angle resolved electron–ion recoil vector correlation study of alternate ion dissociation channels in ? CF3I+

Faraday Discussions Pub Date: 2000-06-01 DOI: 10.1039/B000439L

Abstract

Electron–ion recoil vector correlations are examined for the ionization and subsequent dissociation of ? state CF3I+. The magnitude of the electron and fragment ion recoil vectors permits the energetics of two alternative decays to I+ and CF3+ to be compared, while differences between the angular correlations are interpreted as molecule-frame photoelectron angular distributions which, in the I+ channel, are smeared by molecular rotation between ionization and dissociation. Quantitative estimates of sub-ps I+ decay lifetimes are extracted, indicating very different decay rates for the alternative dissociation channels. Surprisingly, the ka1 and ke photoelectron continua exchange polarization dependence in the I+ channel correlations and vibronic interactions are postulated in explanation. This can also rationalize the non-adiabatic ? CF3I+→I+ decay mechanism and the branching competition between the CF3+ and I+ channels.

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