No Arabic abstract
A phase space boundary between transition and non-transition, similar to those observed in chemical reaction dynamics, is shown experimentally in a macroscopic system. We present a validation of the phase space flux across rank one saddles connecting adjacent potential wells and confirm the underlying phase space conduits that mediate the transition. Experimental regions of transition are found to agree with the theory to within 1%, suggesting the robustness of phase space conduits of transition in a broad array of two or more degree of freedom experimental systems, despite the presence of small dissipation.
We provide a dynamical interpretation of the recently identified `roaming mechanism for molecular dissociation reactions in terms of geometrical structures in phase space. These are NHIMs (Normally Hyperbolic Invariant Manifolds) and their stable/unstable manifolds that define transition states for ion-molecule association or dissociation reactions. The associated dividing surfaces rigorously define a roaming region of phase space, in which both reactive and nonreactive trajectories can be trapped for arbitrarily long times.
We examine the phase space structures that govern reaction dynamics 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 degree 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.
Hamiltonian dynamical systems possessing equilibria of ${saddle} times {centre} times...times {centre}$ 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.
The mechanism for transitions from phase to defect chaos in the one-dimensional complex Ginzburg-Landau equation (CGLE) is presented. We introduce and describe periodic coherent structures of the CGLE, called Modulated Amplitude Waves (MAWs). MAWs of various period P occur naturally in phase chaotic states. A bifurcation study of the MAWs reveals that for sufficiently large period P, pairs of MAWs cease to exist via a saddle-node bifurcation. For periods beyond this bifurcation, incoherent near-MAW structures occur which evolve toward defects. This leads to our main result: the transition from phase to defect chaos takes place when the periods of MAWs in phase chaos are driven beyond their saddle-node bifurcation.
We show that the Olami-Feder-Christensen model exhibits an effective ergodicity breaking transition as the noise is varied. Above the critical noise, the average stress on each site converges to the global average. Below the critical noise, the stress on individual sites becomes trapped in different limit cycles. We use ideas from the study of dynamical systems and compute recurrence plots and the recurrence rate. We identify the order parameter as the recurrence rate averaged over all sites and find numerical evidence that the transition can be characterized by exponents that are consistent with hyperscaling.