Quasi-classical trajectory calculations analyzing the role of bending mode excitations of methane in the Cl + CH4 reaction.

The effects of the methane torsional (nu(2)), umbrella (nu(4)), and the combination nu(2)+nu(4) bending mode excitations on the reactivity and dynamics of the gas-phase Cl + CH(4) --> HCl + CH(3) reaction were analyzed. Quasi-classical trajectory (QCT) calculations, including corrections to avoid zero-point energy leakage along the trajectories, were used on an analytical potential energy surface previously developed by our group. With respect to the reactivity, we found that excitation of either bending mode independently gave similar increases in the reactivity, while the increase observed upon excitation of both modes was larger than the sum of the effect of exciting them independently. Both results agree with recent experimental measures. With respect to the dynamics (rotovibrational and angular distributions of the products), the two bending modes and their combination gave very similar pictures, reproducing the experimental behavior. The satisfactory agreement obtained with a great variety of experimental data (always qualitatively acceptable and sometimes even quantitatively) of the present QCT study lends confidence to the potential energy surface constructed by our group.