Theory of thermal unimolecular reactions at high pressures. II. Analysis of experimental results

Abstract

The simplified version, proposed in Part I, of the statistical adiabatic channel model for thermal unimolecular bond fission reactions and the reverse radical association reactions is applied to 26 experimental systems in which limiting high pressure rate coefficients have been determined. From the analysis, information on the global character of the potential energy surfaces involved is obtained and expressed by the characteristic looseness parameter α of the angular part of the potential and the Morse parameter β of the radial part. It is investigated to what extent empirical ‘‘standard values’’ of α, or of α/β, can be defined, by which limiting high pressure rate coefficients become predictable without knowing further details of the potential energy surfaces.