Trajectory Studies of Model HCC H + C = C Dissociation. III. Details of the Lifetime Distribution Following Chemical Activation
Journal of Chemical Physics
Classical trajectories are used to study the unimolecular decomposition of H–C–C* radicals formed by the H+C=C chemical activation step. The lifetime distribution of the H–C–C* radicals is strongly nonexponential. A long time exponential tail to the lifetime distribution has a unimolecular rate constant ten times smaller than that for a microcanonical ensemble. The relationship between the lifetime distribution and the collision averaged unimolecular rate constant is considered. A discussion is presented on the effect of quasiperiodic trajectories in the molecular phase space on the quantum mechanical unimolecular rate constant.
W L. Hase, Ronald J. Duchovic, K N. Swamy, and R J. Wolf (1984).
Trajectory Studies of Model HCC H + C = C Dissociation. III. Details of the Lifetime Distribution Following Chemical Activation. Journal of Chemical Physics.80 (2), 714-719.