The dynamical significance of valley-ridge inflection points

• Published in: Chemical physics letters 2021-10, Vol.781, p.138970, Article 138970
• Main Authors: García-Garrido, Víctor J., Wiggins, Stephen
• Format: Article
• Language: English
• Subjects: Chemical reaction dynamics; Phase space structure; Post-transition-state bifurcations; Recrossing; Selectivity; Valley-ridge inflection points
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2021.138970

[Display omitted] •Dynamical influence of valley-ridge inflection points on recrossing.•Influence of valley-ridge inflection points on dynamical matching.•Post-transition state bifurcations and dynamical matching.•Post-transition state bifurcations and recrossing. In this paper we demonstrate that valley-ridge inflection (VRI) points of a potential energy surface (PES) have a dynamical influence on the fate of trajectories of the underlying Hamiltonian system. These points have attracted the attention of chemists in the past decades when studying selectivity problems in organic chemical reactions whose energy landscape exhibits a post-transition-state bifurcation in the region between two sequential saddles without an intervening energy minimum. To address the dynamical significance of valley-ridge inflection points, we construct a symmetric potential energy function that allows us to move the location of the VRI point while keeping the locations and energies of the critical points fixed. In this setup, we carry out a parametric study of the dynamical behavior of ensembles of trajectories in terms of the energy of the chemical system and the position of the VRI point. Our analysis reveals that the location of the VRI point controls the fraction of trajectories that recross the high energy saddle region of the PES without entering either of the potential wells that are separated by the low energy saddle.