Quasi-Classical Trajectory Study of NH(³∑^-) + NH(³∑^-) Reactive Collisions

A full-dimension quasi-classical trajectory study of collisions between two NH radicals is presented. Interatomic interactions are represented by a previously reported global six-dimensional potential energy surface for singlet electronic state of the N₂H₂ system. This study suggests that the formation of N₂ from the collision of two NH radicals may occur via a one-step (NH + NH → N₂ + H + H) or two-step (NH + NH → N₂H + H → N₂ + H + H) microscopic reaction mechanism. A fast vibrational energy redistribution is observed in the four-body complex in the latter mechanism. Excitation functions are presented and discussed. A variant of the vibrational energy quantum mechanical threshold method was used to correct the zero-point energy leakage in the classical calculations. The influence of reactant's rotational and vibrational energy on reactivity was investigated by state-specific calculations with one or both reactants excited. Reaction rate constants for the ground and some rotationally excited states are presented using an Arrhenius-Kooij-like functional form.