Regularity in chaotic reaction paths III: Ar-6 local invariances at the reaction bottleneck

Citation
T. Komatsuzaki et Rs. Berry, Regularity in chaotic reaction paths III: Ar-6 local invariances at the reaction bottleneck, J CHEM PHYS, 115(9), 2001, pp. 4105-4117
Citations number
67
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF CHEMICAL PHYSICS
ISSN journal
0021-9606 → ACNP
Volume
115
Issue
9
Year of publication
2001
Pages
4105 - 4117
Database
ISI
SICI code
0021-9606(20010901)115:9<4105:RICRPI>2.0.ZU;2-Z
Abstract
We recently developed a new method to extract a many-body phase-space divid ing surface, across which the transmission coefficient for the classical re action path is unity. The example of isomerization of a 6-atom Lennard-Jone s cluster showed that the action associated with the reaction coordinate is an approximate invariant of motion through the saddle regions, even at mod erately high energies, at which most or all the other modes are chaotic [J. Chem. Phys. 105, 10838 (1999); Phys. Chem. Chem. Phys. 1, 1387 (1999)]. In the present article, we propose a new algorithm to analyze local invarianc es about the transition state of N-particle Hamiltonian systems. The approx imate invariants of motion associated with a reaction coordinate in phase s pace densely distribute in the sea of chaotic modes in the region of the tr ansition state. Using projections of distributions in only two principal co ordinates, one can grasp and visualize the stable and unstable invariant ma nifolds to and from a hyperbolic point of a many-body nonlinear system, lik e those of the one-dimensional, integrable pendulum. This, in turn, reveals a new type of phase space bottleneck in the region of a transition state t hat emerges as the total energy increases, which may trap a reacting system in that region. (C) 2001 American Institute of Physics.