DETAILED DYNAMICS OF COLLINEAR F+H2 TRAJECTORIES

Details of classical trajectory dynamics are analyzed to develop the relationships between classical and quantum results, and between classical and statistical results. A definition of the vibrational energy in the transition region is introduced which allows comparisons to earlier quantum results. Trajectory ensembles are seen to model the quantum wavefunction well in the early stages of the reaction. The failures of trajectory studies are due to wells in the local vibrational levels of the transition states. Action-angle plots and Poincaré surfaces of section display the stochastic behavior of some trajectory sets. This behavior is shown to be predicted by a new quantity, the stochastic impulse integral, which relates trajectory dynamics to the applicability of statistical theories. © 1979 American Institute of Physics.