Phase space structures causing the reaction rate decrease in the collinear hydrogen exchange reaction

DOI10.1007/S10910-019-01083-4MaRDI QIDQ2299059zbMATHOpenAlexWikidataFDO

Authors Vladimír Krajňák, Holger Waalkens

Publication date 20 February 2020

Published in Journal of Mathematical Chemistry (Search for Journal in Brave)

Full work available at URL https://arxiv.org/abs/1911.06240

zbMATH Keywords

invariant manifoldstransition state theoryphase space structuresreaction dynamicshydrogen exchange

Mathematics Subject Classification ID

Classical flows, reactions, etc. in chemistry (92E20)

Abstract: The collinear hydrogen exchange reaction is a paradigm system for understanding chemical reactions. It is the simplest imaginable atomic system with $2$ degrees of freedom modeling a chemical reaction, yet it exhibits behaviour that is still not well understood - the reaction rate decreases as a function of energy beyond a critical value. Using lobe dynamics we show how invariant manifolds of unstable periodic orbits guide trajectories in phase space. From the structure of the invariant manifolds we deduce that insufficient transfer of energy between the degrees of freedom causes a reaction rate decrease. In physical terms this corresponds to the free hydrogen atom repelling the whole molecule instead of only one atom from the molecule. We further derive upper and lower bounds of the reaction rate, which are desirable for practical reasons.

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Cited in

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• Reactive islands for three degrees-of-freedom Hamiltonian systems

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