Trapped Abstraction in the O((1)D) + CHD3 → OH + CD3 Reaction.

Abstract

Despite significant progress made in past decades, it is still challenging to elucidate dynamics mechanisms for polyatomic reactions, in particular, involving complex formation. The reaction of O((1)D) with methane has long been regarded as a prototypical polyatomic system of direct insertion reaction in which the O((1)D) atom can insert into the C-H bond of methane to form a "hot" methanol intermediate before decomposition. Here, we report a combined theoretical and experimental study on the O((1)D) + CHD3 reaction, on which good agreement between theory and experiment is achieved. Our study revealed that this complex-forming reaction actually proceeds via a trapped abstraction mechanism, rather than an insertion mechanism as has long been thought. We anticipate that this reaction mechanism should also be responsible for the reaction of O((1)D) with ethane and propane, as well as many other chemical reactions with deep wells in the interaction region.