The primary step in the ultrafast photodissociation of the methyl iodide dimer

This paper shows the results of combined experimental and theoretical work that have unravelled the mechanism of ultrafast ejection of a methyl group from a cluster, the methyl iodide dimer (CH(3)I)(2). Ab initio calculations have produced optimized geometries for the dimer and energy values and oscillator strengths for the excited states of the A band of (CH(3)I)(2). These calculations have allowed us to describe the blue shift that had been observed in the past in this band. This blue shift has been experimentally determined with higher precision than in all previously reported experiments, since it has been measured through its effect upon the kinetic energy release of the fragments using femtosecond velocity map imaging. Observations of the reaction branching ratio and of the angular nature of the fragment distribution indicate that two main changes occur in A-band absorption in the dimer with respect to the monomer: a substantial change in the relative absorption to different states of the band, and, more importantly, a more efficient non-adiabatic crossing between two of those states. Additionally, time resolved experiments have been performed on the system, obtaining snapshots of the dissociation process. The apparent retardation of more than 100 fs in the dissociation process of the dimer relative to the monomer has been assigned to a delay in the opening of the optical detection window associated with the resonant multiphoton ionization detection of the methyl fragment.