Communication: Transition state theory for dissipative systems without a dividing surface
نویسندگان
چکیده
منابع مشابه
Transition State Theory for dissipative systems without a dividing surface
F. Revuelta, Thomas Bartsch, R. M. Benito, and F. Borondo Grupo de Sistemas Complejos, and Dep. de F́ısica y Mecánica, Escuela Técnica Superior de Ingenieros Agrónomos, Universidad Politécnica de Madrid, 28040 Madrid, Spain Department of Mathematical Sciences, Loughborough University, Loughborough LE11 3TU, United Kingdom Departamento de Qúımica, and Instituto de Ciencias Matemáticas CSIC-UAM-UC...
متن کاملCommunication: transition state theory for dissipative systems without a dividing surface.
Transition state theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when the reactive system is coupled to an environment. The calculations made in this way then overestimate the reaction rate and the results depend critically on...
متن کاملCrossing the dividing surface of transition state theory. II. Recrossing times for the atom-diatom interaction.
We consider a triatomic system with zero total angular momentum and demonstrate that, no matter how complicated the anharmonic part of the potential energy function, classical dynamics in the vicinity of a saddle point is constrained by symmetry properties. At short times and at not too high energies, recrossing dynamics is largely determined by elementary local structural parameters and thus c...
متن کاملTransition-state theory rate calculations with a recrossing-free moving dividing surface.
Two different methods for transition-state theory (TST) rate calculations are presented that use the recently developed notions of the moving dividing surface and the associated moving separatrices: one is based on the flux-over-population approach and the other on the calculation of the reactive flux. The flux-over-population rate can be calculated in two ways by averaging the flux first over ...
متن کاملTransition state theory in liquids beyond planar dividing surfaces
The success of Transition State Theory (TST) in describing the rates of chemical reactions has been less-than-perfect in solution (and sometimes even in the gas phase) because conventional dividing surfaces are only approximately free of recrossings between reactants and products. Recent advances in dynamical systems theory have helped to identify the interconnected manifolds —“superhighways”— ...
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ژورنال
عنوان ژورنال: The Journal of Chemical Physics
سال: 2012
ISSN: 0021-9606,1089-7690
DOI: 10.1063/1.3692182