The dynamical matching mechanism in phase space for caldera-type potential energy surfaces

M. Katsanikas, V. J. García-Garrido, S. Wiggins*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

3 Citations (Scopus)

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.

Original languageEnglish
Article number137199
JournalChemical Physics Letters
Volume743
Early online date8 Feb 2020
DOIs
Publication statusPublished - 16 Mar 2020

Keywords

  • 34C37
  • 34Cxx
  • 70Hxx
  • 70K44
  • Caldera potential energy surface
  • Dynamical matching
  • Heteroclinic trajectories
  • Unstable periodic orbits

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