The Phase Space Mechanism for Selectivity in a Symmetric Potential Energy Surface with a Post-Transition-State Bifurcation

Abstract

Chemical selectivity is a phenomenon displayed by potential energy surfaces (PES) that is relevant for many organic chemical reactions whose PES feature a valley-ridge inflection point (VRI) in the region between two sequential index-1 saddles. In this letter we describe the underlying dynamical phase space mechanism that qualitatively determines the product distributions resulting from bifurcating reaction pathways. We show that selectivity is a consequence of the heteroclinic and homoclinic connections established between the invariant manifolds of the families of unstable periodic orbits (UPOs) present in the system. The geometry of the homoclinic and heteroclininc connections is determined using the technique of Lagrangian descriptors, a trajectory-based scalar technique with the capability of unveiling the geometrical template of phase space structures that characterizes transport.

arXiv comment11 pages, 7 figures

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• From Poincare Maps to Lagrangian Descriptors: The Case of the Valley Ridge Inflection Point Potential
• Tell machine learning potentials what they are needed for: Simulation-oriented training exemplified for glycine
• Tuning the Branching Ratio in a Symmetric Potential Energy Surface with a Post-Transition State Bifurcation using External Time Dependence
• The time evolution of the trajectories after the selectivity in a symmetric potential energy surface with a post-transition-state bifurcation
• Bifurcation Study on a Degenerate Double van der Waals Cirque Potential Energy Surface using Lagrangian Descriptors
• The Influence of a Parameter that Controls the Asymmetry of a Potential Energy Surface with an Entrance Channel and Two Potential Wells
• The Dynamical Significance of Valley-Ridge Inflection Points
• Revealing the phase space structure of Hamiltonian systems using the action