Huang Xia, Cheng Xin-Lu
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, 610065, China.
Key Laboratory of High Energy Density Physics and Technology of Ministry of Education, Sichuan University, Chengdu, 610065, China.
Phys Chem Chem Phys. 2023 Feb 8;25(6):4929-4938. doi: 10.1039/d2cp05329b.
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 NO. A complete database of vibrationally detailed rate coefficients is constructed in a wide temperature range for high vibrational states up to = 25. In particular, the present work shows that the sextet potential energy surface plays a crucial role in the rovibrational relaxation process of O + 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.
我们利用准经典轨迹方法，在新的一氧化氮双重态、四重态和六重态分析势能面上，对分子氧与原子氮之间的非弹性碰撞进行了分子动力学模拟。在高达(v = 25)的高振动状态下，于宽温度范围内构建了一个振动详细速率系数的完整数据库。特别地，目前的工作表明，六重态势能面在氧与氮碰撞的转动振动弛豫过程中起着关键作用。当我们根据相应权重因子考虑该六重态势能面的贡献时，态对态速率系数增加了2至6倍，尤其是在单量子跃迁和/或高温区域的振动能量转移过程中。此外，我们还为该碰撞系统的振动状态特定速率系数提供了阿累尼乌斯型精确拟合，以实现速率系数在涉及空气动力学的数值代码中的灵活应用。我们的结果对于理解具有简并电子态的碰撞系统的弛豫机制具有重要意义。
