Thermal electron attachment to C6F5X and C6H5X (X - I, Br, Cl, and F)

Article abstract of DOI:10.1063/1.465656

Rate constants have been measured for thermal electron attachment to C6F5X (X = I, Br, Cl, F, and H) and C6H5X (X = I, Br, Cl, and F) at room temperature in N2 buffer gas (1-100 Torr) using the pulse-radiolysis microwave cavity method.For all the compounds studied, the rate constants are of the two-body type.Unexpectedly, the values for C6F5X except C6F5H are all the same (ca. 2 x 10^-7 cm³ molecule^-1 s^-1), which are higher than most of the previous values, while that for C6F5H, measured in Xe and Ar buffer gases, is very low (7 x 10^-12 cm³ molecule^-1 s^-1).For C6H5X, the value decreases dramatically with varying X from I to Br to Cl as 1.0 x 10^-8 to 6.5 x 10^-12 to 3 x 10^-14 cm³ molecule^-1 s^-1, and that for C6H5F must be much lower than 10^-13 cm³ molecule^-1 s^-1.These results for the magnitude of the rate constant are rationalized by the variation in the energy of a transient negative-ion state of each molecule, which results from a combination of the electron affinities of constituents (halogen atom X and C6F5 radical) and the strength of the C6F5-X (or C6H5-X) bond.

Full text of DOI:10.1063/1.465656

Thermal electron attachment to C6F5X and C6H5X (X=I, Br, Cl, and F)
Hiroshi Shimamori, Yoshitsugu Tatsumi, and Takeyoshi Sunagawa
Citation: The Journal of Chemical Physics 99, 7787 (1993); doi: 10.1063/1.465656
View online: http://dx.doi.org/10.1063/1.465656
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/99/10?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
28.114.34.22 On: Sat, 22 Nov 2014 11:05:35
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
28.114.34.22 On: Sat, 22 Nov 2014 11:05:35
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
28.114.34.22 On: Sat, 22 Nov 2014 11:05:35
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
28.114.34.22 On: Sat, 22 Nov 2014 11:05:35
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