Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

The N+N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground 4A″ state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N+N2(J=0). The J–K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasiclassical calculation using a London–Eyring–Polanyi–Sato PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate three-dimensional quantal dynamics study for the N+N2 reaction system and the ab initio PES reported here is the ...

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