Specific rate constants k(E, J) for unimolecular bond fissions

Abstract

The specific rate constants k(E, J) for unimolecular bond fission reactions are calculated explicitly by a simplified statistical adiabatic channel model. The input data are reactant and product parameters, together with the ratio α/β of a global looseness parameter α and a Morse parameter β characterizing the intermediate part of the potential surface. Angular momentum coupling restrictions are being accounted for. The approach includes rigid RRKM and loose phase space theory as limiting cases for α/β=0 and α/β≳1, respectively.