A reaction-path dynamics approach to the thermal unimolecular decomposition of acetaldoxime

Abstract The combined approach of the intrinsic reaction coordinate (IRC) and classical trajectory calculations has been used to explain the experimental result in the thermal unimolecular decomposition of acetaldoxime. The IRC calculation indicates that curvature of the reaction path is considerable in the vicinity of s = 0.40 √amu bohr, and in particular that this curvature strongly couples the reaction coordinate to the CCN bending mode. Classical trajectory calculations initiating at this point represent that the trajectories which obtained show enough kinetic energy could bifurcate from the IRC to the course of thermochemically less favorable products.