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arXiv · 2102.10933

Hamiltonian pitchfork bifurcation in transition across index-1 saddles

Wenyang Lyu·Shibabrat Naik·Stephen Wiggins
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Abstract

We study the effect of changes in the parameters of a two-dimensional potential energy surface on the phase space structures relevant for chemical reaction dynamics. The changes in the potential energy are representative of chemical reactions such as isomerization between two structural conformations or dissociation of a molecule with an intermediate. We present a two degrees of freedom quartic Hamiltonian that shows pitchfork bifurcation when the parameters are varied and we derive the bifurcation criteria relating the parameters. Next, we describe the phase space structures - unstable periodic orbits and their associated invariant manifolds, and phase space dividing surfaces - for the systems that can show trajectories undergo reaction defined as crossing of a potential energy barrier. Finally, we quantify the reaction dynamics for these systems by obtaining the directional flux and gap time distribution to illustrate the dependence on total energy and the coupling strength between the two degrees of freedom.

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Wenyang Lyu, Shibabrat Naik, Stephen Wiggins. 2021-02-22. Hamiltonian pitchfork bifurcation in transition across index-1 saddles. https://doi.org/10.1016/j.cnsns.2021.105949

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