Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH 4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode. The H+CH 4 substitution reaction is the simplest reaction occurring via the Walden inversion mechanism. Here, the authors perform a theoretical study of the reaction and uncover the important effect of the umbrella motion of the non-reacting methyl group on the reaction dynamics.