Journal of Physical Chemistry A, Vol.103, No.31, 6106-6113, 1999
Photoelectron and photofragment velocity imaging following the excitation of CH3I to the A-band using fs, ps, and ns laser pulses
Multiphoton processes following the excitation of methyl iodide to the A-band continuum are studied using a pulsed laser beam of 5 eV photons with pulse duration of 15 ns, 5 ps, and 500 fs. Velocity map images are obtained for the resulting photoelectron, I+, and CH3+ fragments. Both one-photon dissociation and multistep ionization are observed, the latter process becoming dominant at the shorter pulse duration. The photoelectron spectra (PES) obtained from velocity map imaging, which provides uniform transmittance for all electron kinetic energies, show that two-photon excitation of CH3I mediated by the dissociative A-band leads to the production of excited CH3I+ ions with non-Franck-Condon intensity distributions. The vibrational distributions obtained are compared with zero kinetic energy (ZEKE) and magnetic bottle PES measurements under similar conditions. Velocity images of the I+ and CH3+ show a marked anisotropy whose angular dependence on the scattering angle varies strongly with the laser pulse duration. At progressively shorter pulse durations, multiphoton ionization/fragmentation of CH3I+ dominates the observed signal.