open access

https://hdl.handle.net/2115/45020

Phase space geometry of dynamics passing through saddle coupled with spatial rotation

英語

2011-02-28

American Institute of Physics

Journal of Chemical Physics

134(8)

084304

Nonlinear reaction dynamics through a rank-one saddle is investigated for many-particle system with spatial rotation. Based on the recently developed theories of the phase space geometry in the saddle region, we present a theoretical framework to incorporate the spatial rotation which is dynamically coupled with the internal vibrational motions through centrifugal and Coriolis interactions. As an illustrative simple example, we apply it to isomerization reaction of HCN with some nonzero total angular momenta. It is found that no-return transition state (TS) and a set of impenetrable reaction boundaries to separate the "past" and "future" of trajectories can be identified analytically under rovibrational couplings. The three components of the angular momentum are found to have distinct effects on the migration of the "anchor" of the TS and the reaction boundaries through rovibrational couplings and anharmonicities in vibrational degrees of freedom. This method provides new insights in understanding the origin of a wide class of reactions with nonzero angular momentum.

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Copyright 2011 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 134, 084304 (2011) and may be found at https://dx.doi.org/10.1063/1.3554906

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