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Relaxation processes and chemical kinetics
Abstract
The role of relaxation processes in determining the rates of activated events has long been a point of discussion in chemical physics. In this paper, we re-examine this issue. We idealize the problem as the classical motion of a particle in a one-dimensional potential coupled to a heat bath. This situation is described by a kinetic equation with a ’’collision operator’’ gℓc. An expansion in powers of the damping constant g is developed. This expansion is not limited to the case of high activation barriers. We compare results for various choices of the collision operator and provide a new derivation of Slater’s new rate theory. A Padé approximant approach unifies our low g results with those in the high g, i.e., diffusive, regime.
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Cites
Handbook of Mathematical Functions
McQuarrie, D. A. (1966) · American Journal of Physics · doi:10.1119/1.1972842 · Cited by 40,433
Cited by
Reaction-rate theory: fifty years after Kramers
Hänggi, P., Talkner, P., & Borkovec, M. (1990) · Reviews of Modern Physics · doi:10.1103/revmodphys.62.251 · Cited by 6,154
Classically exact overlayer dynamics: Diffusion of rhodium clusters on Rh(100)
Voter, A. F. (1986) · Physical Review B · doi:10.1103/physrevb.34.6819 · Cited by 490
Velsko, S. P., Waldeck, D. H., & Fleming, G. R. (1983) · The Journal of Chemical Physics · doi:10.1063/1.444549 · Cited by 306
Campbell, D. M., Mackowiak, M., & Jonas, J. (1992) · The Journal of Chemical Physics · doi:10.1063/1.462019 · Cited by 275
Quantum and classical Fokker-Planck equations for a Gaussian-Markovian noise bath
Tanimura, Y., & Wolynes, P. G. (1991) · Physical Review A · doi:10.1103/physreva.43.4131 · Cited by 224
Self-citation
Metadata
- Authors
- Skinner, J. L., & Wolynes, P. G.
- Venue
- The Journal of Chemical Physics
- Publisher
- AIP Publishing
- Published
- 1978-09-01
- Volume
- 69
- Issue
- 5
- Pages
- 2143-2150
- ISSN
- 0021-9606 (ISSN-L)
- 1089-7690
- OpenAlex
- W2013160138
- Cited by
- 270
- References
- 1
- FWCI
- 13.11
- Type
- journal article
- Language
- en
- Open access
- closed
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- Skinner, J. L., & Wolynes, P. G. (1978). Relaxation processes and chemical kinetics. The Journal of Chemical Physics. https://doi.org/10.1063/1.436814
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Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
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