The role of the sextet potential energy surface in O2 + N inelastic collision processes.

Abstract

We have performed molecular dynamics simulations of inelastic collisions between molecular oxygen and atomic nitrogen, employing the quasi-classical trajectory method on the new doublet, quartet, and sextet analytical potential energy surfaces of NO2. A complete database of vibrationally detailed rate coefficients is constructed in a wide temperature range for high vibrational states up to ν = 25. In particular, the present work shows that the sextet potential energy surface plays a crucial role in the rovibrational relaxation process of O2 + N collisions. The state-to-state rate coefficients increase by a factor of 2 to 6 when we consider the contribution of this sextet potential energy surface according to the corresponding weight factor, especially for vibrational energy transfer processes in single quantum jumps and/or high-temperature regimes. Furthermore, we also provide Arrhenius-type accurate fits for the vibrational state-specific rate coefficients of this collision system to achieve the flexible application of rate coefficients in numerical codes concerning air kinetics. Our results have implications for understanding the relaxation mechanism of the collision system with degenerate electronic states.