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Shortcomings of current theories of non-Markovian activated rate processes (1985)

Straub, John E. ; Borkovec, Michal ; Berne, Bruce J.

College Park, Md. : American Institute of Physics (AIP)

The Journal of Chemical Physics 83 (1985), S. 3172-3174

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ISSN: 1089-7690

Source: AIP Digital Archive

Topics: Physics , Chemistry and Pharmacology

Notes: We calculate the barrier crossing rate constants for a Brownian particle in a double well potential experiencing a non-Markovian friction kernel using full stochastic simulation. We compare the simulation results with recently proposed interpolation formulas which are based on the Grote–Hynes relation and energy diffusion mechanism. We find that such formulas fail in the intermediate regime by orders of magnitude. Therefore we question interpretations of dependence of isomerization rate data on the viscosity based on such ideas.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1063/1.449172

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