Complex Formation in Reactive and Inelastic Scattering: Statistical Adiabatic Channel Model of Unimolecular Processes III

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Abstract
The statistical adiabatic channel model developed previously [25] for unimolecular dissociation reactions is extended to describe bimolecular collisions proceeding via a strongly bound intermediate complex. As examples three cases are considered, in which the intermediate complex corresponds to a known stable molecule: O + O2 → O3*, O + NO → NO2* and Cl + NO → ClNO*. Using known molecular properties and the experimental high pressure recombination rate constants, the specific dissociation rate constants k(E,J), state to state inelastic scattering cross sections σ(v,j → v',j') and center of mass translational energy distributions are calculated with the same simple potential model. Rate constants kvv, for vibrational relaxation are computed and found to be in good agreement with experimental results available for the O + O2 vibrational relaxation. The dependence of cross sections and final state distributions as a function of initial state is illustrated in some detail. Even within the statistical model, there is found to be a marked memory of initial conditions. The range of validity of statistical models is discussed.

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