Competing dissociation channels in the infrared multiphoton decomposition of ethyl vinyl ether

Abstract

Infrared multiphoton decomposition of ethyl vinyl ether (EVE) has been investigated by the crossed laser-molecular beam technique. Competition is observed between the two lowest-energy dissociation channels: (1) EVE → CH3CHO+C2H4, and (2) EVE → CH2CHO+C2H5. Center-of-mass product translational energy distributions were obtained for both dissociation channels. The products of reactions (1) and (2) are formed with mean translational energies of 31 and 5 kcal/mol, respectively. The branching ratio shifts dramatically in favor of the higher energy radical producing channel as the laser intensity and energy fluence are increased, in agreement with the qualitative predictions of statistical unimolecular rate theory.