Time-resolved predissociation of the vibrationless level of the B state of CH3I

The predissociation dynamics of the vibrationless level of the first Rydberg 6s (B (1)E) state of CH(3)I has been studied by femtosecond-resolved velocity map imaging of both the CH(3) and I photofragments. The kinetic energy distributions of the two fragments have been recorded as a function of the pump-probe delay, and as a function of excitation within the umbrella and stretching vibrational modes of the CH(3) fragment. These observations are made by using (2 + 1) Resonant Enhanced MultiPhoton Ionization (REMPI) via the state of CH(3) to detect specific vibrational levels of CH(3). The vibrational branching fractions of the CH(3) are recovered by using the individual vibrationally state-selected CH(3) distributions to fit the kinetic energy distribution obtained by using nonresonant multiphoton ionization of either the I or the CH(3) fragment. The angular distributions and rise times of the two fragments differ significantly. These observations can be rationalized through a consideration of the alignment of the CH(3) fragment and the effect of this alignment on its detection efficiency. Two additional dissociation channels are detected: one associated with Rydberg states near 9.2 eV that were observed previously in photoelectron studies, and one associated with photodissociation of the parent cation around 15 eV.