First-Principles Theory for the Reaction of Chlorine with Methane.

A full-dimensional quantum dynamics simulation of the Cl + CH 4 → HCl + CH 3 reaction based on first-principles theory is reported. Accurate thermal rate constants are calculated, and perfect agreement with experiment is obtained. Despite the heavy atoms present in both reactants, the passage of the reaction barrier is found to occur within only a few tens of femtoseconds. This surprisingly short time scale results from correlated motion of the transferring hydrogen atom and the hydrogen atoms in the methyl fragment which facilitates irreversible barrier passage without relevant participation of heavy atoms. Resonance effects resulting from the heavy-light-heavy characteristics of the reaction system, which were observed in reactive scattering studies, do not affect the thermal rate constant.