Geometrical models of the phase space structures governing reaction dynamics

DOI10.1134/S1560354710010016zbMATH Open1229.37046arXiv0906.4914MaRDI QIDQ653271FDOQ653271

Authors: Stephen Wiggins, Holger Waalkens 

Publication date: 9 January 2012

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

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.

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

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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)

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Cited In (30)

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• 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
• The generalization of the periodic orbit dividing surface in Hamiltonian systems with three or more degrees of freedom. I
• The generalization of the periodic orbit dividing surface for Hamiltonian systems with three or more degrees of freedom -- II
• The chaotic set and the cross section for chaotic scattering in three degrees of freedom
• Bianchi IX dynamics in bouncing cosmologies: homoclinic chaos and the BKL conjecture
• Tilting and squeezing: phase space geometry of Hamiltonian saddle-node bifurcation and its influence on chemical reaction dynamics
• Dynamics associated with the normally hyperbolic invariant manifold that governs the ionization of hydrogen in a circularly polarized electric field
• Bifurcations of normally hyperbolic invariant manifolds in analytically tractable models and consequences for reaction dynamics
• The role of time-dependent phase space structures in reaction dynamics and the no-recrossing property of dividing surfaces
• Finding NHIM: identifying high dimensional phase space structures in reaction dynamics using Lagrangian descriptors
• Direct construction of a dividing surface of minimal flux for multi-degree-of-freedom systems that cannot be recrossed
• The role of depth and flatness of a potential energy surface in chemical reaction dynamics
• Wigner's dynamical transition state theory in phase space: classical and quantum
• Codimension-one partitioning and phase space transport in multi-degree- of-freedom Hamiltonian systems with non-toroidal invariant manifold intersections
• A development scenario connecting the ternary symmetric horseshoe with the binary horseshoe
• 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
• Thirty years of turnstiles and transport
• An algorithm for computing phase space structures in chemical reaction dynamics using Voronoi tessellation
• Reactive islands for three degrees-of-freedom Hamiltonian systems
• Morse bifurcations of transition states in bimolecular reactions
• Dynamics and bifurcations on the normally hyperbolic invariant manifold of a periodically driven system with rank-1 saddle
• Dynamical foundation and limitations of statistical reaction theory
• Phase space structures causing the reaction rate decrease in the collinear hydrogen exchange reaction
• Transition state geometry near higher-rank saddles in phase space

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