Periodic orbit

It is sometimes very usefiil to look at a trajectory such as the synnnetric or antisynnnetric stretch of figure Al.2.5 and figure A1.2.6 not in the physical spatial coordinates (r. . r y), but in the phase space of Hamiltonian mechanics [16, 29], which in addition to the coordinates (r. . r ) also has as additional coordinates the set of conjugate momenta. . pj. ). In phase space, a one-diniensional trajectory such as the aiitisymmetric stretch again appears as a one-diniensional curve, but now the curve closes on itself Such a trajectory is referred to in nonlinear dynamics as a periodic orbit [29]. One says that the aihiamionic nonnal modes of Moser and Weinstein are stable periodic orbits. 

Moser J 1976 Periodic orbits near an equilibrium and a theorem by Alan Weinstein Comm. Pure Appl. Math. 29 727... 

As a result of several complementary theoretical efforts, primarily the path integral centroid perspective [33, 34 and 35], the periodic orbit [36] or instanton [37] approach and the above crossover quantum activated rate theory [38], one possible candidate for a unifying perspective on QTST has emerged [39] from the ideas from [39, 40, 4T and 42]. In this theory, the QTST expression for the forward rate constant is expressed as [39]... 

The classical counterpart of resonances is periodic orbits [91, 95, 96, 97 and 98]. For example, a purely classical study of the H+H2 collinear potential surface reveals that near the transition state for the H+H2 H2+H reaction there are several trajectories (in R and r) that are periodic. These trajectories are not stable but they nevertheless affect strongly tire quantum dynamics. A study of tlie resonances in H+H2 scattering as well as many other triatomic systems (see, e.g., [99]) reveals that the scattering peaks are closely related to tlie frequencies of the periodic orbits and the resonance wavefiinctions are large in the regions of space where the periodic orbits reside. 

Main J, Mandelshtam V A, Wunner G and Taylor H S 1998 Harmonic inversion as a general method for periodic orbit quantization Nonlinearity1015... 

Poliak E 1985 Periodic orbits and the theory of reactive scattering Theory of Chemical Reaction Dynamics vol III, ed M Baer (Boca Raton, FL CRC Press)... 

Schinke R, Weide K, Heumann B and Engel V 1991 Diffuse structures and periodic orbits in the photodissociation of small polyatomic molecules Faraday Discuss. Chem. Soc. 91 31... 

Ezra G S 1996 Periodic orbit analysis of molecular vibrational spectra-spectral patterns and dynamical bifurcations in Fermi resonant systems J. Chem. Phys. 104 26... 

This map has a single quadratic extremum, similar to tliat of tire WR model described in detail earlier. Such maps (togetlier witli tire technical constraint of negative Schwarzian derivative) [23] possess universal properties. In particular, tire universal (U) sequence in which tire periodic orbits appear [24] was observed in tire BZ reaction in accord witli tliis picture of tire chemical dynamics. 

Figure C3.6.5 The first two periodic orbits in the main subhannonic sequence are shown projected onto the (c, C2) plane. This sequence arises from a Hopf bifurcation of the stable fixed point for the parameters given in the text. The arrows indicate the direction of motion, (a) The limit cycle or period-1 orbit at k 2 = 0.11. (b) The first subhannonic or period-2 orbit at k 2 = 0.095.

Figure C3.6.6 The figure shows tire coordinate, for < 0, of tire family of trajectories intersecting tire Poincare surface at cq = 8.5 as a function of bifurcation parameter k 2- As tire ordinate k 2 decreases, tire first subhannonic cascade is visible between k 2 0.1, tire value of tire first subhannonic bifurcation to k 2 0.083, tire subhannonic limit of tire first cascade. Periodic orbits tliat arise by tire tangent bifurcation mechanism associated witli type-I intennittency (see tire text for references) can also be seen for values of k 2 smaller tlian tliis subhannonic limit. The left side of tire figure ends at k 2 = 0.072, tire value corresponding to tire chaotic attractor shown in figure C3.6.1(a). Otlier regions of chaos can also be seen.

This equation shows that only the closed classical trajectories [x(t) = x(0) and x(t) = x(0)] should be taken into account, and the energy spectrum is determined by these periodic orbits [Gutzwiller 1967 Balian and Bloch 1974 Miller 1975a Rajaraman 1975]. 

The original idea of approximating the quantum mechanical partition function by a classical one belongs to Feynman [Feynman and Vernon 1963 Feynman and Kleinert 1986]. Expanding an arbitrary /S-periodic orbit, entering into the partition-function path integral, in a Fourier series in Matsubara frequencies v . 

In fig. 26 the Arrhenius plot ln[k(r)/coo] versus TojT = Pl2n is shown for V /(Oo = 3, co = 0.1, C = 0.0357. The disconnected points are the data from Hontscha et al. [1990]. The solid line was obtained with the two-dimensional instanton method. One sees that the agreement between the instanton result and the exact quantal calculations is perfect. The low-temperature limit found with the use of the periodic-orbit theory expression for kio (dashed line) also excellently agrees with the exact result. Figure 27 presents the dependence ln(/Cc/( o) on the coupling strength defined as C fQ. The dashed line corresponds to the exact result from Hontscha et al. [1990], and the disconnected points are obtained with the instanton method. For most practical purposes the instanton results may be considered exact. 

Fig. 31. Two-dimensional periodic orbits for vibration coupled antisymmetrically to the reaction coordinate. Caustics (C) and take-off points (T) are indicated.

Here we shall describe how the periodic-orbit theory of section 3.4, relating the energy levels with the poles of the spectral function g E), can be extended to two dimensions. For simplicity we shall exemplify this extension by the simplest model in which the total PES is constructed of two paraboloids crossing at some dividing line. Each paraboloid is characterized by two eigenfrequen-cies, o + and [Pg.72]

In accordance with the one-dimensional periodic orbit theory, any orbit contributing to g E) is supposedly constructed from closed classical orbits in the well and subbarrier imaginary-time trajectories. These two classes of trajectories are bordering on the turning points. For the present model the classical motion in the well is separable, and the harmonic approximation for classical motion is quite reasonable for more realistic potentials, if only relatively low energy levels are involved. 

Equation (4.46), however, regardless of the phases i/ , does not describe periodic orbits, unless the frequencies oj are commensurate. Thus the first question that is to be answered is, how to semiclassically quantize a separate well. Furthermore, because of symmetry, a tunneling orbit should pass through the point Q = iQ +, Q-)- However, if it sets out from the turning point at... 

In the parabolic model the equations for caustics are simply Q+ = Q, and Q- = <2-- The periodic orbits inside the well are not described by (4.46), but they run along the borders of the rectangle formed by caustics. It is these trajectories that correspond to topologically irreducible contours on a two-dimensional torus [Arnold 1978] and lead to the quantization condition (4.47). 

The simplest possible attraetor is a fixed point, for which all trajectories starting from the appropriate basin-of-attraction eventually converge onto a single point. For linear dissipative dynamical systems, fixed-point attractors are in fact the only possible type of attractor. Non-linear systems, on the other hand, harbor a much richer spectrum of attractor-types. For example, in addition to fixed-points, there may exist periodic attractors such as limit cycles for two-dimensional flows or doubly periodic orbits for three-dimensional flows. There is also an intriguing class of attractors that have a very complicated geometric structure called strange attractors [ruelleSO],... 

In this way, B preserves the essential dynamical properties of / by preserving orbits i.e., y oB x) = Bof [x). In particular, there is a one-to-one correspondence between repeating symbol sequences in F and periodic orbits of... 

If the interval r is large compared with the time for a collision to be completed (but small compared with macroscopic times), then the arguments of the distribution functions are those appropriate to the positions and velocities before and after a binary collision. The integration over r2 may be replaced by one over the relative distance variable r2 — rx as noted in Section 1.7, collisions taking place during the time r occur in the volume g rbdbde, where g is the relative velocity, and (6,e) are the relative collision coordinates. Incomplete collisions, or motions involving periodic orbits take place in a volume independent of r when Avx(r) and Av2(r) refer to motion for which a collision does not take place (or to the force-field free portion of the... 

The point q = p = 0 (or P = Q = 0) is a fixed point of the dynamics in the reactive mode. In the full-dimensional dynamics, it corresponds to all trajectories in which only the motion in the bath modes is excited. These trajectories are characterized by the property that they remain confined to the neighborhood of the saddle point for all time. They correspond to a bound state in the continuum, and thus to the transition state in the sense of Ref. 20. Because it is described by the two independent conditions q = 0 and p = 0, the set of all initial conditions that give rise to trajectories in the transition state forms a manifold of dimension 2/V — 2 in the full 2/V-dimensional phase space. It is called the central manifold of the saddle point. The central manifold is subdivided into level sets of the Hamiltonian in Eq. (5), each of which has dimension 2N — 1. These energy shells are normally hyperbolic invariant manifolds (NHIM) of the dynamical system [88]. Following Ref. 34, we use the term NHIM to refer to these objects. In the special case of the two-dimensional system, every NHIM has dimension one. It reduces to a periodic orbit and reproduces the well-known PODS [20-22]. 

J. Kaidel, P. Winkler, and M. Brack, Periodic orbit theory for the Henon-Heiles system in the continuum region, Phys. Rev. E 70, 066208 (2004). 

Periodic boundary conditions, Monte Carlo heat flow simulation, nonequilibrium molecular dynamics, 79—81 Periodic-orbit dividing surface (PODS) geometric transition state theory, 196-201 transition state trajectory, 202-213 Perturbation theory, transition state trajectory, deterministically moving manifolds, 224-228... 

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