Dynamic Reaction Path Analysis Based on an Intrinsic Reaction Coordinate

Abstract

<p>We propose two methods that may be used to describe the dynamic reaction path (DRP) based on an intrinsic reaction coordinate (IRC) or minimum energy path, to examine how the actual dynamics proceeds relative to the IRC path. In the first of these, any point on the DRP is expressed in terms of the IRC and the distance from the IRC path. In the second method, any DRP point is expressed in terms of the IRC, the curvature coordinate, and the distance from a two‐dimensional ‘‘reaction plane’’ determined by the IRC path tangent and curvature vectors. The latter representation is based on the fact that the 3<em>N</em>−8 dimensional space orthogonal to the reaction plane is independent of an internal centrifugal force caused by the motion along the IRC path. To analyze the relation between geometrical features of the IRC path and the dynamics, we introduce a function that estimates the variation of the reaction plane along the IRC path. As demonstrations, the methods are applied to the dissociationreaction of thiofolmaldehyde (H₂CS→H₂+CS).</p>