The reaction of F atoms with C2H4. Vibrational Spectrum of the C2H4F Intermediate trapped in solid argon |
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Authors: | Marilyn E Jacox |
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Institution: | Molecular Spectroscopy Division, National Bureau of Standards, Washington, D.C. 20234, USA |
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Abstract: | When the products of the reaction between F atoms produced in a microwave discharge and C2H4 are frozen in a large excess of argon at 14 K, new infrared absorptions appear which can be assigned to the 2-fluoroethyl radical. Studies of the dependence of the product distribution on the F-atom concentration have confirmed that the stabilization of C2H4F2 plays only a minor role under the sampling conditions typical of these experiments. Isotopic substitution experiments have demonstrated that the steric configuration about the CH bond is randomized as a result of the F-atom reaction. Upon irradiation of the sample with the full light of a medium-pressure mercury arc, absorptions of vinyl fluoride and acetylene and of the acetylene—HF complex grow in intensity, while those of FCD2CH2 and of FCH2CD2 diminish in intensity and those of FCH2CH2 a nd of FCH2CD2 are unchanged. The F-atom reactions and photolysis processes which occur in these experiments are discussed, and a tunnelling mechanism is proposed to explain the isotopic selectivity in the 2-fluoroethyl photodecomposition. The vibrational spectrum of FCH2CH2 is compared with that derived in a recent ab initio calculation. |
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