Transition State Theory for dissipative systems without a dividing surface
نویسندگان
چکیده
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-UC3M-UCM, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain
منابع مشابه
Communication: 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...
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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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The fundamental assumption of conventional transition state theory is the existence of a dividing surface having the property that trajectories originating in reactants must cross the surface only once and then proceed to products. Recently it has been shown [1, 2] how to construct a dividing surface in phase space for Hamiltonian systems with an arbitrary (but finite) number of degrees of free...
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The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing-free dividing surface. We show here that it is possible to define such optimal dividing surface in systems with non-Markovian friction. However, a more direct approach to rate calculation is based on invariant manifolds and avoids the use of a dividing surface ...
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Transition state theory (TST) is revisited, as well as evolutions upon TST such as variational TST in which the TST dividing surface is optimized so as to minimize the rate of recrossing through this surface and methods which aim at computing dynamical corrections to the TST transition rate constant. The theory is discussed from an original viewpoint. It is shown how to compute exactly the mean...
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