COLLISION-THEORY TREATMENT OF 3-BODY REACTIONS FORMING N-4+, O-4+, N2O2+, AND N2NO+

Termolecular reactions leading to formation of N4+, O4+, N2 O2+, and N 2 NO+, in the presence of diatomic bath gas, have been modeled by using Langevin-type collision theory to calculate rates of formation and stabilization of the complex ions. The reactions show an interesting trend from RRKM to non-RRKM behavior with decreasing potential well depth for the complex. At the non-RRKM limit the complex lifetime reduces to the duration of an elastic collision between the reactants. The larger negative temperature coefficients of the N2O2+ and N 2NO+ reactions result from dynamical constraints on the total rotational energy of the colliding species. © 1990 American Institute of Physics.