Stereodynamics of the photodissociation of nitromethane at 193 nm: unravelling the dissociation mechanism.

ABSTRACT

The photodissociation of nitromethane at 193 nm is reviewed in terms of new stereodynamical information provided by the measurement of the first four Dixon's bipolar moments, ß0(2)(20), ß0(0)(22), ß0(2)(02), and ß0(2)(22), using slice imaging. The measured speed-dependent ß0(2)(20) (directly related with the spatial anisotropy parameter ß) indicates that after one-photon absorption to the S3(2 (1)A″) state by an allowed perpendicular transition, two reaction pathways can compete with similar probability, a direct dissociation process yielding ground-state CH3 and NO2(1 (2)A2) radicals and a indirect dissociation through conical intersections in which NO2 radicals are formed in lower-lying electronic states. A particularly important result from our measurements is that the low recoil energy part of the methyl fragment translational energy distribution presents a contribution with parallel character, irrespective of the experimental conditions employed, that we attribute to parent cluster dissociation. Moreover, the positive values found for the ß0(0)(22) bipolar moment indicates some propensity for the fragment's recoil velocity and angular momentum vectors to be parallel.