Theory of Thermal Unimolecular Reactions in the Fall‐off Range. II. Weak Collision Rate Constants
Abstract The master equation of thermal unimolecular reactions in the fall‐off range has been solved for a number of representative molecular systems. Weak collision broadening factors F WC ( k 0 / k ∞) are derived and represented empirically. Weak collision efficiencies β c for the low pressure range are calculated for very high temperatures. Combined with earlier representations (part I) of strong collision broadening factors F SC ( k 0 / k ∞), compact empirical expressions for the rate coefficient in the full fall‐off range are proposed. These expressions are useful for data representation and modeling of complex reaction systems which involve isomerization, dissociation and recombination reactions.