The Dynamical Matching Mechanism in Phase Space for Caldera-Type Potential Energy Surfaces

Abstract

Dynamical matching occurs in a variety of important organic chemical reactions. It is observed to be a result of a potential energy surface (PES) having specific geometric features. In particular, a region of relative flatness where entrance and exit to this region is controlled by index-one saddles. Examples of potential energy surfaces having these features are the so-called caldera potential energy surfaces. We develop a predictive level of understanding of the phenomenon of dynamical matching in a caldera potential energy surface. We show that the phase space structure that governs dynamical matching is a particular type of heteroclinic trajectory which gives rise to trapping of trajectories in the central region of the caldera PES. When the heteroclinic trajectory is broken, as a result of parameter variations, then dynamical matching occurs.

arXiv comment9 pages, 2 figures

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• The Influence of a Pitchfork Bifurcation of the Critical Points of a Symmetric Caldera Potential Energy Surface on Dynamical Matching
• Phase space transport in a symmetric Caldera potential with three index-1 saddles and no minima
• Bifurcation of Dividing Surfaces Constructed from Period-Doubling Bifurcations of Periodic Orbits in a Caldera Potential Energy Surface
• Lagrangian Descriptors and the Action Integral of Classical Mechanics
• From Poincare Maps to Lagrangian Descriptors: The Case of the Valley Ridge Inflection Point Potential
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• Bifurcation Study on a Degenerate Double van der Waals Cirque Potential Energy Surface using Lagrangian Descriptors
• The role of depth and flatness of a potential energy surface in chemical reaction dynamics
• Transport and roaming on the Double van der Waals Potential Energy Surface
• Chaos and Regularity in an Anisotropic Soft Squircle Billiard