Transition state theory for solvated reactions beyond recrossing-free dividing surfaces
نویسندگان
چکیده
منابع مشابه
Transition state theory for solvated reactions beyond recrossing-free dividing surfaces.
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 ...
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”— ...
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 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 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 کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Physical Review E
سال: 2016
ISSN: 2470-0045,2470-0053
DOI: 10.1103/physreve.93.062304