Mechanism Change in the Dynamics of the O' + O2 → O'O + O Atom Exchange Reaction at High Collision Energies.

The extreme velocity and the large available energy of atoms with hyperthermal kinetic energies can give rise to novel mechanisms and behavior of chemical reactions unseen at thermal conditions. Crossed-molecular-beams experiments combined with isotope labeling on the reaction of hyperthermal O atoms with O2 molecules have provided an example of the arising complexity of such systems. Quasiclassical trajectory (QCT) calculations proved to be instructive in the exploration of the microscopic mechanism of the reactive and inelastic scattering observed, and a new mechanism has been identified: there are reactive collisions in which the potential energy remains repulsive during the entire encounter ("direct" reactions in which, in a sense, no complex is formed). In this work, the effect of the magnitude of the collision energy on this mechanism is explored. At hyperthermal collision energies, the reaction is characterized by a unique impact parameter window favorable for reaction through complex formation, while the direct collisions take place exclusively at small impact parameters. In direct reactive collisions, contributing as much as 12% to the reaction cross section, first the existing bond is broken, and the new bond is formed afterward. This kind of collision is unique to extremely high collision energies. Analysis of various correlations was used to find out the details of the reaction dynamics. The observed phenomena indicate that when the collision energy is extremely high, one can expect deviation from what an extrapolation from the more familiar energy ranges would predict.