Infrared multiple-photon dissociation of the acetone enol radical cation. Dependence of nonstatistical dissociation on internal energy

Abstract

Infrared multiple-photon dissociation experiments were used to study the energy dependence of the nonstatistical dissociation of the acetone enol cation. This ion isomerizes to the acetone cation, which then loses its methyl groups at unequal rates. We show that the nonstatistical dissociation increases significantly with the energy in excess of the isomerization barrier. The implication is that excitation of a mode (other than the reaction coordinate), in the transition state for isomerization of the acetone enol cation to the acetone cation, affects the amount of nonstatistical reaction