The geometrical structures which regulate transformations in dynamical systems with three or more degrees of freedom (DOFs) form the subject of this paper. Our treatment focuses on the (2n − 3)-dimensional normally hyperbolic invariant manifold (NHIM) in nDOF systems associated with a centre × • • • × centre × saddle in the phase space flow in the (2n − 1)dimensional energy surface. The NHIM bounds a (2n − 2)-dimensional surface, called a 'transition state' (TS) in chemical reaction dynamics, which partitions the energy surface into volumes characterized as 'before' and 'after' the transformation. This surface is the long-sought momentum-dependent TS beyond two DOFs. The (2n − 2)-dimensional stable and unstable manifolds associated with the (2n − 3)-dimensional NHIM are impenetrable barriers with the topology of multidimensional spherical cylinders. The phase flow interior to these spherical cylinders passes through the TS as the system undergoes its transformation. The phase flow exterior to these spherical cylinders is directed away from the TS and, consequently, will never undergo the transition. The explicit forms of these phase space barriers can be evaluated using normal form theory. Our treatment has the advantage of supplying a practical algorithm, and we demonstrate its use on a strongly coupled nonlinear Hamiltonian, the hydrogen atom in crossed electric and magnetic fields.
Recent developments in Transition State Theory brought about by dynamical systems theory are extended to time-dependent systems such as laser-driven reactions. Using time-dependent normal form theory, we construct a reaction coordinate with regular dynamics inside the transition region. The conservation of the associated action enables one to extract time-dependent invariant manifolds that act as separatrices between reactive and non-reactive trajectories and thus make it possible to predict the ultimate fate of a trajectory. We illustrate the power of our approach on a driven Hénon-Heiles system, which serves as a simple example of a reactive system with several open channels. The present generalization of Transition State Theory to driven systems will allow one to study processes such as the control of chemical reactions through laser pulses.
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