Phase space conduits for reaction in multidimensional systems: HCN isomerization in three dimensions

H Waalkens, AD Burbanks, S Wiggins

Research output: Contribution to journalArticle (Academic Journal)peer-review

91 Citations (Scopus)

Abstract

The three-dimensional hydrogen cyanide/isocyanide isomerization problem is taken as an example to present a general theory for computing the phase space structures which govern classical reaction dynamics in systems with an arbitrary (finite) number of degrees of freedom. The theory, which is algorithmic in nature, comprises the construction of a dividing surface of minimal flux which is locally a "surface of no return." The theory also allows for the computation of the global phase space transition pathways that trajectories must follow in order to react. The latter are enclosed by the stable and unstable manifolds of a so-called normally hyperbolic invariant manifold (NHIM). A detailed description of the geometrical structures and the resulting constraints on reaction dynamics is given, with particular emphasis on the three degrees of freedom case. A procedure is given which uses these structures to compute orbits homoclinic to, and heteroclinic between, NHIMs. The role of homoclinic and heteroclinic orbits in global recrossings of dividing surfaces and transport in complex systems is explained. The complete description provided here is inherently one within phase space; it cannot be inferred from a configuration space picture. A complexification of the classical phase space structures to incorporate quantum effects is also discussed. The results presented here call into question certain assumptions routinely made on the global dynamics; this paper provides methods that enable one to understand and quantify the phase space dynamics of reactions without making such assumptions. (C) 2004 American Institute of Physics.
Translated title of the contributionPhase space conduits for reaction in multidimensional systems: HCN isomerization in three dimensions
Original languageEnglish
Pages (from-to)6207 - 6225
Number of pages19
JournalJournal of Chemical Physics
Volume121 (13)
DOIs
Publication statusPublished - 1 Oct 2004

Bibliographical note

Publisher: American Institute of Physics
Other identifier: IDS Number: 857VE

Fingerprint Dive into the research topics of 'Phase space conduits for reaction in multidimensional systems: HCN isomerization in three dimensions'. Together they form a unique fingerprint.

Cite this