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In this paper we study the breakdown of normal hyperbolicity and its consequences for reaction dynamics; in particular, the dividing surface, the flux through the dividing surface (DS), and the gap time distribution. Our approach is to study these questions using simple, two degree-of-freedom Hamiltonian models where calculations for the different geometrical and dynamical quantities can be carried out exactly. For our examples, we show that resonances within the normally hyperbolic invariant manifold may, or may not, lead to a `loss of normal hyperbolicity. Moreover, we show that the onset of such resonances results in a change in topology of the dividing surface, but does not affect our ability to define a DS. The flux through the DS varies continuously with energy, even as the energy is varied in such a way that normal hyperbolicity is lost. For our examples the gap time distributions exhibit singularities at energies corresponding to the existence of homoclinic orbits in the DS, but these singularities are not associated with loss of normal hyperbolicity.
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We study reaction dynamics on a model potential energy surface exhibiting post-transition state bifurcation in the vicinity of a valley ridge inflection point. We compute fractional yields of products reached after the VRI region is traversed, both with and without dissipation. It is found that apparently minor variations in the potential lead to significant changes in the reaction dynamics. Moreover, when dissipative effects are incorporated, the product ratio depends in a complicated and highly non-monotonic fashion on the dissipation parameter. Dynamics in the vicinity of the VRI point itself play essentially no role in determining the product ratio, except in the highly dissipative regime.
It is known that the asymptotic invariant manifolds around an unstable periodic orbit in conservative systems can be represented by convergent series (Cherry 1926, Moser 1956, 1958, Giorgilli 2001). The unstable and stable manifolds intersect at an infinity of homoclinic points, generating a complicated homoclinic tangle. In the case of simple mappings it was found (Da Silva Ritter et al. 1987) that the domain of convergence of the formal series extends to infinity along the invariant manifolds. This allows in practice to study the homoclinic tangle using only series. However in the case of Hamiltonian systems, or mappings with a finite analyticity domain,the convergence of the series along the asymptotic manifolds is also finite. Here, we provide numerical indications that the convergence does not reach any homoclinic points. We discuss in detail the convergence problem in various cases and we find the degree of approximation of the analytical invariant manifolds to the real (numerical) manifolds as i) the order of truncation of the series increases, and ii) we use higher numerical precision in computing the coefficients of the series. Then we introduce a new method of series composition, by using action-angle variables, that allows the calculation of the asymptotic manifolds up to an a arbitrarily large extent. This is the first case of an analytic development that allows the computation of the invariant manifolds and their intersections in a Hamiltonian system for an extent long enough to allow the study of homoclinic chaos by analytical means.
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.
Unstable periodic orbits (UPOs) are a valuable tool for studying chaotic dynamical systems. They allow one to extract information from a system and to distill its dynamical structure. We consider here the Lorenz 1963 model with the classic parameters value and decompose its dynamics in terms of UPOs. We investigate how a chaotic orbit can be approximated in terms of UPOs. At each instant, we rank the UPOs according to their proximity to the position of the orbit in the phase space. We study this process from two different perspectives. First, we find that, somewhat unexpectedly, longer period UPOs overwhelmingly provide the best local approximation to the trajectory, even if our UPO-detecting algorithm severely undersamples them. Second, we construct a finite-state Markov chain by studying the scattering of the forward trajectory between the neighbourhood of the various UPOs. Each UPO and its neighbourhood are taken as a possible state of the system. We then study the transitions between the different states. Through the analysis of the subdominant eigenvectors of the corresponding stochastic matrix we provide a novel interpretation of the mixing processes occurring in the system by taking advantage of the concept of quasi-invariant sets.
In this study, we analyze how changes in the geometry of a potential energy surface in terms of depth and flatness can affect the reaction dynamics. We formulate depth and flatness in the context of one and two degree-of-freedom (DOF) Hamiltonian normal form for the saddle-node bifurcation and quantify their influence on chemical reaction dynamics. In a recent work, Garcia-Garrido, Naik, and Wiggins illustrated how changing the well-depth of a potential energy surface (PES) can lead to a saddle-node bifurcation. They have shown how the geometry of cylindrical manifolds associated with the rank-1 saddle changes en route to the saddle-node bifurcation. Using the formulation presented here, we show how changes in the parameters of the potential energy control the depth and flatness and show their role in the quantitative measures of a chemical reaction. We quantify this role of the depth and flatness by calculating the ratio of the bottleneck-width and well-width, reaction probability (also known as transition fraction or population fraction), gap time (or first passage time) distribution, and directional flux through the dividing surface (DS) for small to high values of total energy. The results obtained for these quantitative measures are in agreement with the qualitative understanding of the reaction dynamics.
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