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Microscopic friction and solvation in barrier crossing: isomerization of stilbene in size-selected hexane clusters

Heikal, A. A. and Chong, S. H. and Baskin, J. S. and Zewail, A. H. (1995) Microscopic friction and solvation in barrier crossing: isomerization of stilbene in size-selected hexane clusters. Chemical Physics Letters, 242 (4-5). pp. 380-389. ISSN 0009-2614. doi:10.1016/0009-2614(95)00781-X. https://resolver.caltech.edu/CaltechAUTHORS:20160825-074653263

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Abstract

In order to understand the roles of bulk friction and solvation in barrier crossing reactions, here we report our first study of the isomerization rates for a beam of t-stilbene-hexane_n clusters, n = 1–5, at excess energies covering the range E_(ex) = 0–4000 cm^(−1). We observe that rates measured at excess energies well above the t-stilbene isomerization barrier decrease monotonically with increasing number of solvent molecules. The influence of microscopic solvation on the rates is systematically studied and related to changes in barrier height and internal friction, both key to the understanding of behavior in the bulk.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1016/0009-2614(95)00781-XDOIArticle
http://www.sciencedirect.com/science/article/pii/000926149500781XPublisherArticle
Additional Information:© 1995 Elsevier Science B.V. Received 9 June 1995; in final form 27 June 1995. This work is supported by a grant from the National Science Foundation. It is a pleasure to acknowledge the stimulating theoretical discussion with Rudy Marcus, and the helpful remarks of the referee.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics9101
Issue or Number:4-5
DOI:10.1016/0009-2614(95)00781-X
Record Number:CaltechAUTHORS:20160825-074653263
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160825-074653263
Official Citation:A.A. Heikal, S.H. Chong, J.S. Baskin, A.H. Zewail, Microscopic friction and solvation in barrier crossing: isomerization of stilbene in size-selected hexane clusters, Chemical Physics Letters, Volume 242, Issues 4–5, 25 August 1995, Pages 380-389, ISSN 0009-2614, http://dx.doi.org/10.1016/0009-2614(95)00781-X. (http://www.sciencedirect.com/science/article/pii/000926149500781X)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:69922
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:26 Aug 2016 16:47
Last Modified:11 Nov 2021 04:21

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