Ab initio study on thermal dissociation of diazo compounds

Abstract

The thermal dissociation processes of diazomethane and 2-diazo-1-acetaldehyde were studied by ab initio computations with 3-21G and 6-31G ∗ basis sets, using the CN bond as the reaction axis. The geometries were optimized, and the correlation energies were taken into account by doing a single-point, fourth-order Møller-Plesset calculation (MP4//6-31G ∗). The results show that, owing to the substitution of the carbonyl group, the N-C-C group is no longer a linear structure. The corresponding dissociation process is more like a “single-bond breakage”, and a negative dissociation energy was calculated from SCF plus correlation energies, which means that this dissociation process is energetically favourable.