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Picosecond dissociation of ketene: Experimental state-to-state rates and tests of statistical theories

Potter, E. D. and Gruebele, M. and Khundkar, L. R. and Zewail, A. H. (1989) Picosecond dissociation of ketene: Experimental state-to-state rates and tests of statistical theories. Chemical Physics Letters, 164 (5). pp. 463-470. ISSN 0009-2614. http://resolver.caltech.edu/CaltechAUTHORS:20160831-091534634

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Abstract

The state-to-state dissociation rates of ketene have been measured for a variety of singlet methylene rotational states in both the ground and (010) vibrational levels of the methylene fragment. Measured time constants range from 1.0 ns at 500 cm^(−1) to 19 ps at 5600 cm^(−1) above threshold. The measurements cannot be accounted for by simple phase space theory (PST), which has been used to explain product state distributions, or tight transition state RRKM theory, but are in good agreement with variational RRKM theory. The estimated threshold rate of 2×10^8 s^(−1) is in agreement with the previous lower limit of 7×10^7 s^(−1) of Chen, Green and Moore.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/0009-2614(89)85239-XDOIArticle
http://www.sciencedirect.com/science/article/pii/000926148985239XPublisherArticle
Additional Information:© 1990 Elsevier Science Publishers B.V. Received 29 September 1989; in final form 5 October 1989. The authors would like to thank Professor Rudolph A. Marcus for helpful discussions, and Professor C. Bradley Moore for many helpful discussions and correspondence of unpublished results. We would also like to thank Amy Hoffman for assistance with some of the (000) measurements. This work was supported by a grant from the National Science Foundation CHE 8512887.
Funders:
Funding AgencyGrant Number
NSFCHE-8512887
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Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics8039
Record Number:CaltechAUTHORS:20160831-091534634
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160831-091534634
Official Citation:E.D. Potter, M. Gruebele, L.R. Khundkar, A.H. Zewail, Picosecond dissociation of ketene: Experimental state-to-state rates and tests of statistical theories, Chemical Physics Letters, Volume 164, Issue 5, 22 December 1989, Pages 463-470, ISSN 0009-2614, http://dx.doi.org/10.1016/0009-2614(89)85239-X. (http://www.sciencedirect.com/science/article/pii/000926148985239X)
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ID Code:70061
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:31 Aug 2016 17:47
Last Modified:31 Aug 2016 17:47

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