Reaction dynamics study of O-+C2H2 with crossed beams and density-functional theory calculations

The reactions between O- and C2H2 have been studied using the crossed-beam technique and density-functional theory (DFT) calculations in the collision energy range from 0.35 to 1.5 eV (34-145 kJ/mol). Both proton transfer and C-O bond formation are observed. The proton transfer channel forming C2H- is the dominant pathway. The center-of-mass flux distributions of the C2H- product ions are highly asymmetric, with maxima close to the velocity and direction of the precursor acetylene beam, characteristic of direct reactions. The reaction quantitatively transforms the entire reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the proton is transferred in a configuration in which both the breaking and the forming bonds are extended. The C-O bond formation channel producing HC2O- displays a distinctive kinematic picture in which the product distribution switches from predominantly forward scattering with a weak backward peak to sideways scattering as the collision energy increases. At low collision energies, the reaction occurs through an intermediate that lives a significant fraction of a rotational period. The asymmetry in the distribution leads to a lifetime estimate of 600 fs, in reasonable agreement with DFT calculations showing that hydrogen-atom migration is rate limiting. At higher collision energies, the sideways-scattered products arise from repulsive energy release from a bent transition state. (C) 2005 American Institute of Physics.