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Solvent dynamics-modified RRKM theory in clusters

Marcus, R. A. (1995) Solvent dynamics-modified RRKM theory in clusters. Chemical Physics Letters, 244 (1-2). pp. 10-18. ISSN 0009-2614. doi:10.1016/0009-2614(95)00899-F.

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Kramers and RRKM theories are used to formulate a solvent dynamics-modified treatment of unimolecular reaction rates in clusters. The canonical Kramers' description is modified so as to apply to microcanonical systems. An entropic gradient, arising from all coordinates but the reaction coordinate q, and a q-dependent microcanonical vibrational temperature are introduced. A simple expression is obtained relating the rate constant to its RRKM value and permitting comparison with recent experiments. An application is also made to the Kramers' turnover region.

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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1995 Elsevier Science B.V. Received 17 July 1995; in final form 28 July 1995. It is a pleasure to acknowledge stimulating discussions with my colleague, Ahmed Zewail, which prompted this work. It is also a pleasure to acknowledge the helpful comments of my student, Xueyu Song, and the support of this research by the National Science Foundation and the Office of Naval Research.
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Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:1-2
Record Number:CaltechAUTHORS:20150408-065026591
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Official Citation:R.A. Marcus, Solvent dynamics-modified RRKM theory in clusters, Chemical Physics Letters, Volume 244, Issues 1–2, 29 September 1995, Pages 10-18, ISSN 0009-2614, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56449
Deposited By: Tony Diaz
Deposited On:08 Apr 2015 23:07
Last Modified:10 Nov 2021 20:59

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