Abstract
We have reported previously an example of dynamics-driven reaction pathway, in which ab initio MD trajectory shows a different pathway from the intrinsic reaction coordinate on the potential energy surface. Thus, for the intramolecular rearrangement of pinacolyl system, the MD trajectory suggested a stepwise pathway whereas a concerted mechanism was suggested by IRC. Such dynamics-driven reaction pathway can be viewed as resulting from asynchronicity of two reaction modes, in this specific case the C-O stretching and C-C-C bending modes. Similar phenomena may occur in many other organic reactions, in which multiple intramolecular or intermolecular modes are involved in the reaction coordinate. Generality of such mode asynchronicity will be discussed for various types of reactions, including the Beckmann rearrangements and proton transfer reactions on the basis of MO and MD computations.
