Nonstatistical inversion dynamics of T-shaped Ar3. II. Separatrix transition states Journal Articles uri icon

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abstract

  • T-shaped Ar3 inversion population dynamics is treated in terms of separatrix transition states and flux–flux correlation formalism. Observed numerical population decays exhibit oscillations which are modeled statistically using a four species mechanism. Successful models are based on the generalized absorbing boundary method, and a statistical approximation for two of the four required gap distributions. The statistical rate constants essential to the latter approximations are obtained via Monte Carlo integration together with short time trajectory computations. The delayed lifetime gap model provided excellent model gap distributions, in contrast to previous results [R. S. Dumont and S. Jain, J. Chem. Phys. 97, 1227 (1992)] based on the primitive transition state. However, it is an essential ingredient of the model population decays.

publication date

  • November 15, 1993