Geometrical models of the phase space structures governing reaction dynamics

DOI10.1134/S1560354710010016MaRDI QIDQ653271zbMATH OpenFDO

Authors Stephen Wiggins, Holger Waalkens

Publication date 9 January 2012

Published in Regular and Chaotic Dynamics (Search for Journal in Brave)

Full work available at URL https://arxiv.org/abs/0906.4914

zbMATH Keywords

normally hyperbolic invariant manifoldtransition state theorychemical reaction dynamicshigh dimensional Hamiltonian dynamicsphase space structure and geometryPoincaré-Birkhoff normal form theory

Mathematics Subject Classification ID

Hamilton's equations (70H05) Classical flows, reactions, etc. in chemistry (92E20) Applications of dynamical systems (37N99)

Abstract: Hamiltonian dynamical systems possessing equilibria of $saddleimescentreimes\mathrm{...}imescentre$ stability type display emph{reaction-type dynamics} for energies close to the energy of such equilibria; entrance and exit from certain regions of the phase space is only possible via narrow emph{bottlenecks} created by the influence of the equilibrium points. In this paper we provide a thorough pedagogical description of the phase space structures that are responsible for controlling transport in these problems. Of central importance is the existence of a emph{Normally Hyperbolic Invariant Manifold (NHIM)}, whose emph{stable and unstable manifolds} have sufficient dimensionality to act as separatrices, partitioning energy surfaces into regions of qualitatively distinct behavior. This NHIM forms the natural (dynamical) equator of a (spherical) emph{dividing surface} which locally divides an energy surface into two components (`reactants' and `products'), one on either side of the bottleneck. This dividing surface has all the desired properties sought for in emph{transition state theory} where reaction rates are computed from the flux through a dividing surface. In fact, the dividing surface that we construct is crossed exactly once by reactive trajectories, and not crossed by nonreactive trajectories, and related to these properties, minimizes the flux upon variation of the dividing surface. We discuss three presentations of the energy surface and the phase space structures contained in it for 2-degree-of-freedom (DoF) systems in the threedimensional space $R^3$, and two schematic models which capture many of the essential features of the dynamics for $n$-DoF systems. In addition, we elucidate the structure of the NHIM.

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Cited in

(30)

• Phase-space geometry and reaction dynamics near index 2 saddles
• Phase space structures governing reaction dynamics in rotating molecules
• Local geometric structures and bifurcations of a polynomial differential system from a general multi-molecular reaction
• Partial barriers to chaotic transport in 4D symplectic maps
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• The phase space geometry underlying roaming reaction dynamics
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• The geometry of reaction dynamics
• The role of normally hyperbolic invariant manifolds (NHIMS) in the context of the phase space setting for chemical reaction dynamics
• A development scenario connecting the ternary symmetric horseshoe with the binary horseshoe
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