Finding Minimum Structures on the Seam of Crossing in Reactions of Type A + B → X: Exploration of Nonadiabatic Ignition Pathways of Unsaturated Hydrocarbons.

A new theoretical approach is proposed for finding automatically minimum structures on the seam of crossing (MSX) in reactions of type A + B → X, where the artificial-force-induced reaction (AFIR) method is combined with the seam model function (SMF) approach. Its application to reactions between triplet dioxygen and unsaturated hydrocarbons provided many MSX structures. In addition to known ignition pathways, we discovered a pathway through a new type of MSX in the reaction of dioxygen with aromatic hydrocarbons; for benzene, this new pathway requires a lower energy than those of three known ignition pathways and is likely to be the most important. This demonstrates that the AFIR-SMF approach has the ability to discover unknown/unexpected MSX structures without prejudice for presumed pathways or mechanisms.