Phase space dynamics of bimolecular reactions and the breakdown of transition state theory

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Abstract
We investigate the phase structure of the reaction H+H2 restricted to collinear geometry. When variational transition state theory is exact, the phase space structure is relatively simple and a phase space approach is in agreement with this theory which is centered in configuration space. At energies where variational transition state theory breaks down, a phase space approach leads to the resolution of an interaction region. All trajectories which violate transition state theory enter this region during their propagation. In addition, all trajectories which are not violations miss the region. The resolution of the interaction region allows us to model the reaction even at energies where variational transition state theory fails by up to a factor of 2. The phase space approach also defines conditions under which variational transition state theory is exact which are stronger than those previously put forth. Other aspects of the reaction dynamics which can be understood from the phase space dynamics are also discussed in this paper.