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

Mauguière, Frédéric A. L., Collins, Peter, Kramer, Zeb C., Carpenter, Barry K. ORCID:, Ezra, Gregory S., Farantos, Stavros C. and Wiggins, Stephen 2016. Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone. Journal of Chemical Physics 144 (5) , 054107. 10.1063/1.4940798

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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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Advanced Research Computing @ Cardiff (ARCCA)
Subjects: Q Science > QD Chemistry
Additional Information: PDF uploaded in accordance with publisher's policies at (accessed 4.2.16).
Publisher: American Institute of Physics
ISSN: 0021-9606
Funders: NSF/EPSRC
Date of First Compliant Deposit: 30 March 2016
Date of Acceptance: 7 January 2016
Last Modified: 04 May 2023 14:02

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