CaltechAUTHORS
  A Caltech Library Service

Femtosecond Activation of Reactions and the Concept of Nonergodic Molecules

Diau, Eric W.-G. and Herek, Jennifer L. and Kim, Zee Hwan and Zewail, Ahmed H. (1998) Femtosecond Activation of Reactions and the Concept of Nonergodic Molecules. Science, 279 (5352). pp. 847-851. ISSN 0036-8075. https://resolver.caltech.edu/CaltechAUTHORS:20141125-110318227

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20141125-110318227

Abstract

The description of chemical reaction dynamics often assumes that vibrational modes are well coupled (ergodic) and redistribute energy rapidly with respect to the course of the reaction. To experimentally probe nonergodic, nonstatistical behavior, studies of a series of reactions induced by femtosecond activation for molecules of varying size but having the same reaction coordinates [CH_2 − (CH_2)_(n – 2) − C = O† → products, with n = 4, 5, 6, and 10] were performed. Comparison of the experimental results with theoretical electronic structure and rate calculations showed a two to four orders of magnitude difference, indicating that the basic assumption of statistical energy redistribution is invalid. These results suggest that chemical selectivity can be achieved with femtosecond activation even at very high energies.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science.279.5352.847DOIArticle
http://www.sciencemag.org/content/279/5352/847PublisherArticle
Additional Information:© 1998 American Association for the Advancement of Science. Received 14 October 1997; accepted 5 December 1997. Supported by a grant from the Office of Naval Research and by the NSF. We thank R. Bersohn for communicating unpublished results to us and S. Baskin for helpful discussions.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
NSFUNSPECIFIED
Issue or Number:5352
Record Number:CaltechAUTHORS:20141125-110318227
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141125-110318227
Official Citation:Femtosecond Activation of Reactions and the Concept of Nonergodic Molecules Eric W.-G. Diau, Jennifer L. Herek, Zee Hwan Kim, and Ahmed H. Zewail Science 6 February 1998: 279 (5352), 847-851. [DOI:10.1126/science.279.5352.847]
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52144
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Nov 2014 20:15
Last Modified:03 Oct 2019 07:39

Repository Staff Only: item control page