A theoretical analysis of the reaction of H with C 2H 5

Abstract

The interaction of H with C2H5 is analyzed at the CAS+1+2 level using a correlation-consistent polarized valence double zeta basis set. These ab initio calculations show three barrierless pathways two leading to association and one for abstraction. The association channels are substantially more attractive than the abstraction one and thus dominate the kinetics. An analytic representation of the ab initio data is implemented in a variable reaction coordinate transition state theory study of the temperature dependence of the association kinetics. These theoretical estimates for the high pressure association rate constant are directly compared with related experimental measurements in an effort to resolve the discrepancy between recent and earlier results.