Dynamics of insertion reactions of H2 molecules with excited atoms

Recent progress in the study of insertion reactions of hydrogen molecules with excited atoms is reviewed in this article. In particular, the dynamics of the reaction of O(1D), N(2D), C(1D), and S(1D) with H2 and its isotopomers, which have received a great deal of attention over the past decade, are examined in detail. All of these systems have in common the existence of several potential energy surfaces (PES) correlating with the reagents' states, and consequently, they can give rise to reaction following different adiabatic and nonadiabatic pathways. The main contribution, however, arises from their ground singlet PESs which feature the existence of deep wells with small or null barriers for insertion. Accordingly, these reactions proceed mainly via formation of relatively long-lived collision complexes and display an overall nearly statistical behavior. In spite of their similarities, the various reactions have peculiar characteristics caused by important differences of their respective PESs. The contribution of excited PES to the global reactivity, which has also become an important issue and a challenge both for theory and experiment, is also examined. The different theoretical approaches are discussed in the text, along with the experimental results obtained by a variety of techniques. The recent exact quantum treatments of these reactive systems together with the development of a rigorous statistical model have contributed to a very accurate description which in many cases matches very well the detailed measurements. The quasi-classical trajectory (QCT) method has also provided a fairly accurate description of the reaction dynamics for these systems. In particular, the analysis in terms of collision times has yielded interesting clues about the reaction mechanisms.