Classical trajectory simulations of post-transition state dynamics

Classical chemical dynamics simulations of post-transition state dynamics are reviewed. Most of the simulations involve direct dynamics for which the potential energy and gradient are obtained directly from an electronic structure theory. The chemical reaction attributes and chemical systems presented are product energy partitioning for Cl- center dot center dot center dot CH3Br- -> ClCH3 + Br- and C2H5F -> C2H4 + HF dissociation, non-RRKM dynamics for cyclopropane stereomutation and the Cl center dot center dot center dot CH3Cl complexes mediating the Cl- + CH3Cl S(N)2 nucleophilic substitution reaction, and non-IRC dynamics for the OH- + CH3F and F- + CH3OOH chemical reactions. These studies illustrate the important role of chemical dynamics simulations in understanding atomic-level reaction dynamics and interpreting experiments. They also show that widely used paradigms and model theories for interpreting reaction kinetics and dynamics are often inaccurate and are not applicable.