Geometrical Models of the Phase Space Structures Governing Reaction Dynamics

Hamiltonian dynamical systems possessing equilibria of saddle x center x ... x center stability type display 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 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 Normally Hyperbolic Invariant Manifold (NHIM), whose 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) 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 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 three-dimensional 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.