Kim, Sang Kyu and Pedersen, Soren and Zewail, Ahmed H. (1995) Direct femtosecond observation of the transient intermediate in the α-cleavage reaction of (CH_3)_2CO to 2CH_3+CO: Resolving the issue of concertedness. Journal of Chemical Physics, 103 (1). pp. 477-480. ISSN 0021-9606. doi:10.1063/1.469614. https://resolver.caltech.edu/CaltechAUTHORS:20160825-074654292
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Abstract
When a reaction involving two equivalent bonds has sufficient energy to break both of them, it can proceed by either a concerted or a stepwise mechanism. For Norrish type‐I and other reactions, this issue has been controversial since direct time resolution of the individual C–C cleavage events was not possible. Here, for the elementary α‐cleavage of acetone, we report on the femtosecond resolution of the intermediates using mass spectrometry. The results show the nonconcertedness of the reaction, provide the times for the primary and secondary C–C breakage, and indicate the role of electronic structure (σ^*, antibonding impulse) and the vibrational motions involved.
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| Additional Information: | © 1995 American Institute of Physics. Received 17 April 1995; accepted 2 May 1995. This research was supported by a grant from the Air Force Office of Scientific Research and by the National Science Foundation. We wish to thank Professor Y. T. Lee for providing us with a preprint of their recent work, Jennifer Herek for the helpful discussion, and Dr. W. P. Hess for communicating the ab initio results. | |||||||||
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| Issue or Number: | 1 | |||||||||
| DOI: | 10.1063/1.469614 | |||||||||
| Record Number: | CaltechAUTHORS:20160825-074654292 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20160825-074654292 | |||||||||
| Official Citation: | Direct femtosecond observation of the transient intermediate in the α‐cleavage reaction of (CH3)2CO to 2CH3+CO: Resolving the issue of concertedness Kim, Sang Kyu and Pedersen, Soren and Zewail, Ahmed H., The Journal of Chemical Physics, 103, 477-480 (1995), DOI:http://dx.doi.org/10.1063/1.469614 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 69926 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 26 Aug 2016 17:53 | |||||||||
| Last Modified: | 11 Nov 2021 04:21 |
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