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An approach to reaction path branching using valley–ridge inflection points of potential-energy surfaces

Research paper by Wolfgang Quapp, Michael Hirsch, Dietmar Heidrich

Indexed on: 04 Mar '04Published on: 04 Mar '04Published in: Theoretical Chemistry Accounts



Abstract

Valley–ridge inflection (VRI) points of a potential-energy surface (PES) may have a strong relation to the occurrence of bifurcations along reaction pathways of molecular rearrangements. We discuss two different definitions of VRI points in the literature. The calculation of symmetric VRI points has already been reported [W. Quapp et al. (1998) Theor. Chem. Acc. 100: 285–299]. Here, we in addition calculate special asymmetric VRI points which are placed on gradient extremals (GE). Following a GE opens the possibility to find the VRI point on it. An application is presented to search for asymmetric VRI points near the isomerization valley of the PES of the HCN molecule. A new method for GE-following is based on a mathematical connection between the following of a reduced gradient and the calculation of GEs. The tangent search method to follow a GE to the smallest eigenvalue [W. Quapp et al. (2000) Theor. Chem. Acc. 105: 145–155] is extended to follow also GEs to higher eigenvalues in order to find a VRI point. The new method needs gradient and second derivatives of the PES only.