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.

9 pages, 2 figures

References in corpus (3)

• A Theoretical Framework for Lagrangian Descriptors
• Nonstatistical dynamics on the caldera
• Finding NHIM: Identifying High Dimensional Phase Space Structures in Reaction Dynamics using Lagrangian Descriptors

Cited by in corpus (3)

• The Nature of Reactive and Non-reactive Trajectories for a Three Dimensional Caldera Potential Energy Surface
• The Influence of a Pitchfork Bifurcation of the Critical Points of a Symmetric Caldera Potential Energy Surface on Dynamical Matching
• From Poincare Maps to Lagrangian Descriptors: The Case of the Valley Ridge Inflection Point Potential