Chaos long-time dynamics

In coimection with the energy transfer modes, an important question, to which we now turn, is the significance of classical chaos in the long-time energy flow process, in particnlar the relative importance of chaotic classical dynamics, versus classically forbidden processes involving dynamical tuimelling . 

Intramolecular dynamics and chemical reactions have been studied for a long time in terms of classical models. However, many of the early studies were restricted by the complexities resulting from classical chaos, Tlie application of the new dynamical systems theory to classical models of reactions has very recently revealed the existence of general bifurcation scenarios at the origin of chaos. Moreover, it can be shown that the infinite number of classical periodic orbits characteristic of chaos are topological combinations of a finite number of fundamental periodic orbits as determined by a symbolic dynamics. These properties appear to be very general and characteristic of typical classical reaction dynamics. 

What we should stress here is that the Hamiltonian H(p, x, n, Sj does not take a nearly integrable form, since h p,x) admits an arbitrary nonlinear system. Thus, it can generate strong chaos as a whole. Even in such a case the authors showed that the perturbation theory with respect to an appropriate small parameter can be applied, and they proved under certain conditions that exponentially long-time stability can be seen in the dynamics if suitably chosen variables are monitored. 

The notion of chaos is interwoven with the discussion of time evolution, which we do not pursue in this volume. It is worthwhile, however, to note that it is, by now, well understood that a quantum-mechanical system with a finite Hamiltonian matrix cannot satisfy many of the purely mathematical characterizations of chaos. Equally, however, over long periods of time such systems can manifest many of the qualitative features that one associates with classically chaotic systems. It is not our intention to follow this most interesting theme. Instead we seek a more modest aim, namely, to forge a link between the elementary notions of classical nonlinear dynamics and the algebraic approach. This turns out to be possible using the action-angle variables of classical mechanics. In this section we consider only the nonlinear dynamics aspects. We complete the bridge in Chapter 7. 

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