An angle resolved electron-ion recoil vector correlation study of alternate ion dissociation channels in (A)over-tilde CF3I+

Electron-ion recoil vector correlations are examined for the ionization and subsequent dissociation of (A) over tilde 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 ka(1) 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 (A) over tilde CF3I+ --> I+ decay mechanism and the branching competition between the CF3+ and I+ channels.