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  Electron attachment to CF3 and CF3Br at temperatures up to 890 K: Experimental test of the kinetic modeling approach.

Shuman, N. S., Miller, T. M., Viggiano, A. A., & Troe, J. (2013). Electron attachment to CF3 and CF3Br at temperatures up to 890 K: Experimental test of the kinetic modeling approach. The Journal of Chemical Physics, 138(20): 204316. doi:10.1063/1.4807606.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0014-5F01-5 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0028-9498-D
Genre: Journal Article

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Shuman, N. S., Author
Miller, T. M., Author
Viggiano, A. A., Author
Troe, J.1, Author              
Affiliations:
1Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society, ou_578625              

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 Abstract: Thermal rate constants and product branching fractions for electron attachment to CF3Br and the CF3 radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF3Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF3Br measurement was made using standard techniques, and the CF3 measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF3Br proceeds exclusively by the dissociative channel yielding Br-, with a rate constant increasing from 1.1 x 10(-8) cm(3) s(-1) at 300 K to 5.3 x 10(-8) cm(3) s(-1) at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF3 attachment proceeds through competition between associative attachment yielding CF3- and dissociative attachment yielding F-. Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only similar to 5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach.

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Language(s): eng - English
 Dates: 2013-05-31
 Publication Status: Published online
 Pages: 7
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1063/1.4807606
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Title: The Journal of Chemical Physics
Source Genre: Journal
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Pages: - Volume / Issue: 138 (20) Sequence Number: 204316 Start / End Page: - Identifier: -