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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.
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 w
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 i
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
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
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 nor