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Abstract
Reactive scattering of O atoms with C2F4 molecules has been studied at an initial translational energy E = 36 kJ mol-1 using a supersonic beam of O atoms seeded in He. Velocity distributions of F2CO product were measured at the FCO+ mass peak by cross-correlation time-of-flight analysis. A full contour map of the differential reaction cross-section has been obtained which favours the forward hemisphere. The average product translational energy represents only a small fraction f′av = 0·10 of the total energy available to products in their ground electronic states but is slightly greater than that predicted for a long-lived collision complex. These results are consistent with the Cvetanovic mechanism whereby reaction proceeds via a diradical intermediate in which the O atom remains bonded to one C atom of the C2F4 molecule. However, the lifetime of the diradical intermediate is comparable to its rotational period due to the reaction exoergicity which is large even for the formation of the electronically excited CF2 (3 B 1) radical. These results are consistent with the ready formation of triplet CF2 (3 B 1) product but do not preclude the formation of singlet CF2 (1 A 1) following a triplet-singlet transition.
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