Title: Infrared spectrum of the 2-chloroethyl radical in solid para-hydrogen
Authors: Amicangelo, Jay C.
Golec, Barbara
Bahou, Mohammed
Lee, Yuan-Pern
Department of Applied Chemistry
Institute of Molecular science
Issue Date: 2012
Abstract: The addition reaction of chlorine with ethylene (C(2)H(4)) is expected to proceed via a free radical intermediate, the 2-chloroethyl radical, however, this intermediate has not been previously observed spectroscopically. Irradiation at 365 nm of a co-deposited mixture of Cl(2), C(2)H(4), and p-H(2) at 3.2 K produces a series of new lines in the infrared spectrum. A strong line at 664.0 cm(-1) and weaker lines at 562.1, 1069.9, 1228.0, 3041.1 and 3129.3 cm(-1) are concluded to be due to a single carrier based on their behavior upon subsequent annealing to 4.5 K and secondary irradiation at 254 and 214 nm. The positions and intensities of these lines agree with the MP2/aug-cc-pVDZ predicted vibrational spectrum of the 2-chloroethyl ((center dot)CH(2)CH(2)Cl) radical. In order to confirm this assignment, isotopic experiments were performed with C(2)D(4) and t-C(2)H(2)D(2) and the corresponding infrared bands due to the deuterium isotopomers of this radical ((center dot)CD(2)CD(2)Cl and (center dot)C(2)H(2)D(2)Cl) have been observed. A final set of experiments were performed following irradiation of the Cl(2)/C(2)H(4)/p-H(2) mixture at 365 nm, in which the matrix was irradiated with filtered infrared light from a globar source, which has been shown to induce reactions between isolated Cl atoms and matrix H(2) to produce HCl and H atoms. In these experiments, the major products observed were HCl, the ethyl radical (center dot C(2)H(5)) and ethyl chloride (C(2)H(5)Cl) and the possible mechanisms for the formation of these species are discussed.
URI: http://hdl.handle.net/11536/15301
ISSN: 1463-9076
DOI: 10.1039/c1cp22524c
Volume: 14
Issue: 2
Begin Page: 1014
End Page: 1029
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