The general approach to classical unimolecular reaction rates due to Thiele is revisited in light of recent advances in the phase space formulation of transition state theory for multidimensional systems. Key concepts, such as the phase space dividing surface separating reactants from products, the average gap time, and the volume of phase space associated with reactive trajectories, are both rigorously defined and readily computed within the phase space approach. We analyze in detail the gap time distribution and associated reactant lifetime distribution for the isomerization reaction HCN=CNH, previously studied using the methods of phase space transition state theory. Both algebraic (power law) and exponential decay regimes have been identified. Statistical estimates of the isomerization rate are compared with the numerically determined decay rate. Correcting the RRKM estimate to account for the measure of the reactant phase space region occupied by trapped trajectories results in a drastic overestimate of the isomerization rate. Compensating but as yet not fully understood trapping mechanisms in the reactant region serve to slow the escape rate sufficiently that the uncorrected RRKM estimate turns out to be reasonably accurate, at least at the particular energy studied. Examination of the decay properties of subensembles of trajectories that exit the HCN well through either of two available symmetry related product channels shows that the complete trajectory ensemble effectively attains the full symmetry of the system phase space on a short time scale t0.5 ps, after which the product branching ratio is 1:1, the “statistical” value. At intermediate times, this statistical product ratio is accompanied by nonexponential (nonstatistical) decay. We point out close parallels between the dynamical behavior inferred from the gap time distribution for HCN and nonstatistical behavior recently identified in reactions of some organic molecules.
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