Published September 29, 1995
| public
Journal Article
Solvent dynamics-modified RRKM theory in clusters
- Creators
-
Marcus, R. A.
Abstract
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.
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.Additional details
- Eprint ID
- 56449
- Resolver ID
- CaltechAUTHORS:20150408-065026591
- NSF
- Office of Naval Research (ONR)
- Created
-
2015-04-08Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field