We present a crossed molecular beam study of the reactions of C+with CH4over the relative energy range from 0.66 to 2.38 eV. CH+3production involves a direct rebound collision mechanism. Production of C2H+3and C2H+2proceeds through unimolecular decay of longhyphen;lived collision complexes. Hydrogen atom emission proceeds through a rotating ethylene cation and yields a polarized angular distribution of reaction products. The kinetic energy distributions for vinyl cation production place nearly three times as much of the available energy in translation as a statistical model predicts. At low collision energy, C2H+2production proceeds through molecular hydrogen elimination and the angular distribution for reaction products is polarized perpendicularly to the initial relative velocity vector. At a higher collision energy of 2.38 eV, the complex decays in a fraction of a rotational period. The lifetime of 0.03 ps inferred from the asymmetry in the angular distribution is in good agreement with a statistical calculation incorporating nonadiabatic couplings among the excited and ground states of C2H+4. The recoil distribution at this energy is dramatically narrower than at the lower collision energy and is consistent with the sequential ejection of two hydrogen atoms through a metastable C2H+3intermediate.
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