Multiple Transition States and Roaming in Ion-Molecule Reactions: a Phase Space Perspective

Abstract

We provide a dynamical interpretation of the recently identified `roaming' mechanism for molecular dissociation reactions in terms of geometrical structures in phase space. These are NHIMs (Normally Hyperbolic Invariant Manifolds) and their stable/unstable manifolds that define transition states for ion-molecule association or dissociation reactions. The associated dividing surfaces rigorously define a roaming region of phase space, in which both reactive and nonreactive trajectories can be trapped for arbitrarily long times.

20 pages, 6 figures

References in corpus (2)

• Wigner's Dynamical Transition State Theory in Phase Space: Classical and Quantum
• Microcanonical rates, gap times, and phase space dividing surfaces

Cited by in corpus (15)

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• Phase-space resolved rates in driven multidimensional chemical reactions
• Morse bifurcations of transition states in bimolecular reactions
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• Roaming at Constant Kinetic Energy: Chesnavich's Model and the Hamiltonian Isokinetic Thermostat
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• Predicting trajectory behaviour via machine-learned invariant manifolds
• Roaming in acetaldehyde