Dissociation of Small Molecules: Direct Dissociation or Statistical Energy Redistribution ?

Article abstract of DOI:10.1021/j100365a022

Dissociative processes in highly excited small molecules and radicals are studied by translational spectroscopy.Fragmentation reactions are identified, and insight into their mechanisms is gained by the differential measurement of the fragment kinetic energy.The reactions under study are induced by dissociative charge exchange.The dissociation of CH3Cl with an internal energy between 6.1 and 6.9 eV into CH3. + Cl. proceeds via a repulsive surface, converting most available energy into kinetic energy.The dissociation of CH3CO. with an internal energy above 1.9 eV into CH3. + CO is preceded by energy scrambling The kinetic energy release is governed by the dynamics of the reaction: a simple kinematic model for the conversion of bending motion into fragment translation is consistent with the measured spectra.