Bottlenecks to vibrational energy flow in OCS: Structures and mechanisms

Details Bottlenecks to vibrational energy flow in OCS: Structures and mechanisms Bottlenecks to vibrational energy flow in OCS: Structures and mechanisms

2008-11-27

arxiv.org/abs/0811.4563v1

J. Chem. Phys. 130, 164105 (2009)

Physics

Chemical Physics

13 pages, 13 figures

Scientific paper

10.1063/1.3103219

Finding the causes for the nonstatistical vibrational energy relaxation in the planar carbonyl sulfide (OCS) molecule is a longstanding problem in chemical physics: Not only is the relaxation incomplete long past the predicted statistical relaxation time, but it also consists of a sequence of abrupt transitions between long-lived regions of localized energy modes. We report on the phase space bottlenecks responsible for this slow and uneven vibrational energy flow in this Hamiltonian system with three degrees of freedom. They belong to a particular class of two-dimensional invariant tori which are organized around elliptic periodic orbits. We relate the trapping and transition mechanisms with the linear stability of these structures.

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