with methane: the effects of bending momentum, ruling out the precursor mechanism, and steps toward ''Polanyi rules'' for polyatomic reactionsw

Quasi-classical trajectories for the hydrogen abstraction (HA) reaction C2H2 1 þ CH4 - C2H3 1 þ CH3, were analyzed to probe the mechanistic origins of the large, mode-specific reactivity enhancement observed experimentally following excitation of the C2H2 1 cis-bending mode. The trajectories show the correct trend in reactivity vs. CC stretch and bending excitations, and also reproduce the experimental recoil velocity map. Analysis of the trajectories shows that at collision energy of 0.5 eV hydrogen abstraction is dominated by a direct mechanism, but B15% of the reaction is mediated by a precursor complex. The vibrational enhancement mostly comes from direct collisions. The bending vibration enhances the reactivity in two ways. Collisions in bent geometries (of C2H2 1 ) are more reactive; however, the dominant vibrational effect is a consequence of the momentum associated with the bending vibration. Enhancement by vibrational momentum is reminiscent of the behavior seen by Polanyi and co-workers for late barrier A þ BC reactions, and indeed, the atom transfer event in the C2H2 1 þ CH4 system does occur late in the collision. We, therefore, explore the possibilities for interpreting polyatomic vibrational dynamics in a ‘‘Polanyi Rule’’ context, using trajectories to guide the construction of a reduced dimensionality surface.