Influence of Vibrational Excitation on the Reaction of F- with CH3I: Spectator Mode Behavior, Enhancement, and Suppression.

Detailed insight into chemical reaction dynamics can be obtained by probing the effect of mode-specific vibrational excitation. Suppression or enhancement of reactivity is possible as is already known from the Polanyi rules. In the reaction F- + CH3I, we found vibrational enhancement, suppression, and spectator mode dynamics in the four different reaction channels. For this system we have probed the influence of symmetric CH-stretching vibration over a collision energy range of 0.7-2.3 eV. Proton transfer is significantly enhanced, while for the nucleophilic substitution channel the spectator mode dynamics at lower collision energies unexpectedly move toward enhancement at higher collision energies. In contrast, for two halide abstraction channels, forming FI- and FHI-, we found an overall suppression, which stems mainly from a suppression of the FHI- product. We compare these results to quasiclassical trajectory calculations and with the sudden vector projection model.