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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. doi:10.1126/science.279.5352.847.

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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.

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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 We thank R. Bersohn for communicating unpublished results to us and S. Baskin for helpful discussions.
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Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:5352
Record Number:CaltechAUTHORS:20141125-110318227
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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
Deposited By: Tony Diaz
Deposited On:25 Nov 2014 20:15
Last Modified:10 Nov 2021 19:21

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