Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone

Frederic A L Mauguiere, Peter R C Collins, Zeb C Kramer, Barry Carpenter, Gregory Ezra, Stavros Farantos, Stephen R Wiggins

Research output: Contribution to journalArticle (Academic Journal)peer-review

20 Citations (Scopus)
355 Downloads (Pure)

Abstract

We examine the phase space structures that govern reactiondynamics in the absence of critical points on the potential energy surface. We show that in the vicinity of hyperbolic invariant tori, it is possible to define phase space dividing surfaces that are analogous to the dividing surfaces governing transition from reactants to products near a critical point of the potential energy surface. We investigate the problem of capture of an atom by a diatomic molecule and show that a normally hyperbolic invariant manifold exists at large atom-diatom distances, away from any critical points on the potential. This normally hyperbolic invariant manifold is the anchor for the construction of a dividing surface in phase space, which defines the outer or loose transition state governing capture dynamics. We present an algorithm for sampling an approximate capture dividing surface, and apply our methods to the recombination of the ozone molecule. We treat both 2 and 3 degrees of freedom models with zero total angular momentum. We have located the normally hyperbolic invariant manifold from which the orbiting (outer) transition state is constructed. This forms the basis for our analysis of trajectories for ozone in general, but with particular emphasis on the roaming trajectories.
Original languageEnglish
Article number054107
Number of pages12
JournalJournal of Chemical Physics
Volume144
Early online date3 Feb 2016
DOIs
Publication statusPublished - 7 Feb 2016

Keywords

  • Ozone
  • Phase space methods
  • Potential energy surfaces
  • Oscillators
  • Surface dynamics

Fingerprint Dive into the research topics of 'Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone'. Together they form a unique fingerprint.

Cite this