Tunnelling in cyclocarbenes: An application of Semiclassical Transition State Theory in reduced dimensions

Abstract

Methods to calculate rates of chemical reactions ab initio, in reduced dimensions, using Semiclassical Transition State Theory have recently been formulated. Here we further develop its application to unimolecular reactions where the choice of active degrees of freedom is not clear a priori. We describe in more detail a procedure to determine which degrees of freedom must be accounted for explicitly in the reduced dimensionality framework, and illustrate its success on a hydrogen transfer reaction of a cyclocarbene species.