Marcus, R. A. (1996) Solvent dynamics: Modified Rice–Ramsperger–Kassel–Marcus theory. II. Vibrationally assisted case. Journal of Chemical Physics, 105 (13). pp. 5446-5454. ISSN 0021-9606. doi:10.1063/1.472385. https://resolver.caltech.edu/CaltechAUTHORS:MARjcp96
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Abstract
Expressions are given for a solvent dynamics-modified Rice–Ramsperger–Kassel–Marcus (RRKM) theory for clusters. The role of vibrational assistance across the transition state region is included. The usual differential equation for motion along the slow coordinate X in constant temperature systems is modified so as to apply to microcanonical systems. A negative entropy term, –Sv(X), replaces the (1/T)∂U/∂X or (1/T)∂G/∂X which appears in canonical systems. Expressions are obtained for the RRKM-type rate constant k(X) and for the Sv(X) which appear in the differential equation. An approximate solution for steady-state conditions is given for the case that the "reaction window" is narrow. The solution then takes on a simple functional form. The validity of the assumption can be checked a posteriori. Recrossings of the transition state are included and the condition under which the treatment approaches that in Part I is described.
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| Additional Information: | © 1996 American Institute of Physics. Received 21 March 1996; accepted 27 June 1996. It is a pleasure to acknowledge the support of the National Science Foundation and the Office of Naval Research in the support of this research, and to thank a reviewer for thoughtful comments. | |||||||||
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| Subject Keywords: | ACTIVATED-RATE-PROCESSES; ELECTRON-TRANSFER REACTIONS; TRANSITION-STATE THEORY; FREQUENCY-DEPENDENT FRICTION; DIFFUSION-CONTROLLED REACTIONS; SLOW CONFORMATIONAL-CHANGES; CHEMICAL-REACTION DYNAMICS; NON-DEBYE SOLVENTS; NONEQUILIBRIUM SOLVATION; REACTION COORDINATE | |||||||||
| Issue or Number: | 13 | |||||||||
| DOI: | 10.1063/1.472385 | |||||||||
| Record Number: | CaltechAUTHORS:MARjcp96 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:MARjcp96 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 11076 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 02 Jul 2008 | |||||||||
| Last Modified: | 01 Jun 2023 22:59 |
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