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The Validity of the "Diradical" Hypothesis: Direct Femtosecond Studies of the Transition-State Structures

Pedersen, S. and Herek, J. L. and Zewail, A. H. (1994) The Validity of the "Diradical" Hypothesis: Direct Femtosecond Studies of the Transition-State Structures. Science, 266 (5189). pp. 1359-1364. ISSN 0036-8075. https://resolver.caltech.edu/CaltechAUTHORS:20150116-150955716

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Abstract

Direct studies of diradicals, the molecular species hypothesized to be archetypal of chemical bond transformations in many classes of reactions, have been made using femtosecond laser techniques with mass spectrometry in a molecular beam. These studies are aimed at "freezing" the diradicals in time and in the course of the reaction. The passage of these species through the transition-state region was observed and the effect of total energy and alkyl substitution on the rates of bond closure and cleavage was examined. The results establish the nature of these intermediates and define their existence during reactions.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science.266.5189.1359 DOIArticle
http://www.sciencemag.org/content/266/5189/1359PublisherArticle
http://www.jstor.org/stable/2884930JSTORArticle
Additional Information:© 1994 American Association for the Advancement of Science. 26 August 1994; accepted 23 September 1994. Supported by a grant from the Air Force Office of Scientific Research and by the National Science Foundation. We are grateful to P. B. Dervan, D. A. Dougherty, M. Okumura, J. D. Roberts, and W. von. E. Doering for the helpful discussions. We thank J. A. Berson and B. K. Carpenter for their helpful suggestions and penetrating questions, C. Doubleday Jr. for his interest in this work and for communicating unpublished results, K. Anderson for the preparation of 2,2,5,5-tetramethylcyclopentanone, and L. Banares for his help in the preliminary work (bulb studies) in this group. Contribution no. 8970 from the Arthur Amos Noyes Laboratory of Chemical Physics.
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Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
NSFUNSPECIFIED
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Other Numbering System NameOther Numbering System ID
Caltech Division of Chemistry and Chemical Engineering8970
Issue or Number:5189
Record Number:CaltechAUTHORS:20150116-150955716
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150116-150955716
Official Citation:Pedersen, S., Herek, J. L., & Zewail, A. H. (1994). The Validity of the "Diradical" Hypothesis: Direct Femtoscond Studies of the Transition-State Structures. Science, 266(5189), 1359-1364. doi: 10.1126/science.266.5189.1359
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53843
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:17 Jan 2015 03:14
Last Modified:03 Oct 2019 07:53

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