Dynamical system theory Hamiltonian systems

According to dynamical systems theory, the escape rate is given by the difference (92) between the sum of positive Lyapunov exponents and the Kolmogorov-Sinai entropy. Since the dynamics is Hamiltonian and satisfies Liouville s theorem, the sum of positive Lyapunov exponents is equal to minus the sum of negative ones ... 

Hamiltonian dynamical system theory is the mathematical framework on which TST rests many textbooks, of various mathematical sophistication, describe this branch of pure/applied mathematics. Some of the various flavors are [20-24]. Very little of this vast information will be needed here, and we shall try to be as self-consistent as possible. 

Extension toward the fully nonlinear case is straightforward for 1-DOF Hamiltonians. The energy conservation relation H p,q) = E allows us to dehne (explicitly or implicitly) p = p q E), thereby reducing the ODE to a simple quadrature. In this procedure there is no problem of principle (unlike the n >2-DOE case). It works in practice also, and it is possible to adapt Eigs. 3-5 to the nonlinear regime. It must be underlined that besides that simple procedure, we present a theorem in dynamical system theory (containing Hamiltonian dynamics as a particular case). This theorem is valid for n DOEs (hence for n = 1) it relates the full dynamics to the linearized dynamics, called tangent dynamics in the mathematical literature. 

The classical microscopic description of molecular processes leads to a mathematical model in terms of Hamiltonian differential equations. In principle, the discretization of such systems permits a simulation of the dynamics. However, as will be worked out below in Section 2, both forward and backward numerical analysis restrict such simulations to only short time spans and to comparatively small discretization steps. Fortunately, most questions of chemical relevance just require the computation of averages of physical observables, of stable conformations or of conformational changes. The computation of averages is usually performed on a statistical physics basis. In the subsequent Section 3 we advocate a new computational approach on the basis of the mathematical theory of dynamical systems we directly solve a... 

It is not possible to discuss highly excited states of molecules without reference to the recent progress in nonlinear dynamics.2 Indeed, the stimulation is mutual. Rovibrational spectra of polyatomic molecules provides both an ideal testing ground for the recent ideas on the manifestation of chaos in Hamiltonian systems and in turn provides many challenges for the theory. 

The phase space structure of classical molecular dynamics is extensively used in developing classical reaction rate theory. If the quanmm reaction dynamics can also be viewed from a phase-space perspective, then a quantum reaction rate theory can use a significant amount of the classical language and the quantum-classical correspondence in reaction rate theory can be closely examined. This is indeed possible by use of, for example, the Wigner function approach. For simplicity let us consider a Hamiltonian system with only one DOF. Generalization to many-dimensional systems is straightforward. The Wigner function associated with a density operator /)( / is defined by... 

It is a phase space rather than configuration space theory, so it can treat Hamiltonian systems containing unconserved angular momenta like Coriolis interactions which prevent the Hamiltonian from being written as a sum of the kinetic and potential energies [6,18]. The resulting hypersurfaces are dynamical in that they involve momenta as well as coordinates. 

Until now, we have discussed NHIMs in general dynamical systems. In this section, we limit our argument to Hamiltonian systems and show how singular perturbation theory works. In particular, we discuss NHIMs in the context of reaction dynamics. First, we explain how NHIMs appear in conventional reaction theory. Then, we will show that Lie permrbation theory applied to the Hamiltonian near a saddle with index 1 acmally transforms the equation of motion near the saddle to the Fenichel normal form. This normal form can be considered as an extension of the Birkhoff normal form from stable fixed points to saddles with index 1 [2]. Finally, we discuss the transformation near saddles with index larger than 1. 

In addition to computer simulations, what drives the research in this direction is elaborated perturbation theories developed almost simultaneously. In particular, the Kolmogorov-Arnold-Moser (KAM) theorem, which has shown the existence of invariant tori under a small perturbation to completely inte-grable systems, and the Nekhoroshev theorem, which has proved exponentially long-time stability of trajectories close to completely integrable ones, are landmarks in this field. Although a lot of works have been done, there still remain unsolved important questions, and the Hamiltonian system is being studied as one of important branches in the theory of dynamical systems [3-5]. 

In Section VII we conclude our results and discuss several issues arising from our proposals. We revisit our original motivation—that is, to find a simple model, in the sense of dynamical systems, that captures several common aspects of slow dynamics in liquid water, or more generally supercooled liquids or glasses. Our attempt is to make clear the relation and compatibility between the potential energy landscape picture and phase space theories in the Hamiltonian dynamics. Importance of heterogeneity of the system is discussed in several respects. Unclarified and unsolved points that still remain but should be considered as crucial issues in slow dynamics in molecular systems are listed. 

Hamiltonian systems are fundamental to classical mechanics they provide an equivalent but more geometric version of Newton s laws. They are also central to celestial mechanics and plasma physics, where dissipation can sometimes be neglected on the time scales of interest. The theory of Hamiltonian systems is deep and beautiful, but perhaps too specialized and subtle for a first course on nonlinear dynamics. See Arnold (1978), Lichtenberg and Lieberman (1992), Tabor (1989), or Henon (1983) for introductions. 

In the recent past, analytical research in Celestial Mechanics has centred on KAM theory and its applications to the dynamics of low dimensional Hamiltonian systems. Results were used to interpret observed solutions to three body problems. Order was expected and chaos or disorder the exception. Researchers turned to the curious exception, designing analytical models to study the chaotic behaviour at resonances and the effects of resonant overlaps. Numerical simulations were completed with ever longer integration times, in attempts to explore the manifestations of chaos. These methods improved our understanding but left much unexplained phenomena. 

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