Calculating reaction path of a bifurcation reaction is often difficult because the transition states do not lead to the products in such reactions. Typically, the transition state leads to anoter transition state which then follow a ridge until a valley ridge inflexion (VRI) point on the potential energy surface. At the VRI path splits into two leading to two products. The traditional transition-state based methods for finding the reaction path are not applicable for bifurcation reaction. We have applied a recently proposed method to compute the bifurcation reaction paths for the reaction: H3CO -> H2COH. The method relies on solving an eikonal equation using the fast-marching algorithm proposed by James Sethian. Our results include a variety of reaction paths: least-action path, least energy path, least-time path. The method opens the possibility of computing the important sampling points on the potential energy surface, much the way it is done in Monte Carlo sampling method.

Computing reaction paths of bifurcating reactions: An action-wave-front based perspective

243rd National Meeting (2012)

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