Konings Maarten, Desrousseaux Benjamin, Lique François, Loreau Jérôme
KU Leuven, Division of Quantum Chemistry and Physical Chemistry, Department of Chemistry, Celestijnenlaan 200F, 3001 Leuven, Belgium.
Université de Rennes 1, CNRS, IPR (Institut de Physique de Rennes) - UMR 6251, F-35000 Rennes, France.
J Chem Phys. 2021 Sep 14;155(10):104302. doi: 10.1063/5.0062388.
Inelastic collisions and elementary chemical reactions proceeding through the formation and subsequent decay of an intermediate collision complex, with an associated deep well on the potential energy surface, pose a challenge for accurate fully quantum mechanical approaches, such as the close-coupling method. In this study, we report on the theoretical prediction of temperature-dependent state-to-state rate coefficients for these complex-mode processes, using a statistical quantum method. This statistical adiabatic channel model is benchmarked by a direct comparison using accurate rate coefficients from the literature for a number of systems (H + H, HD + H, SH + H, and CH + H) of interest in astrochemistry and astrophysics. For all of the systems considered, an error of less than factor 2 was found, at least for the dominant transitions and at low temperatures, which is sufficiently accurate for applications in the above mentioned disciplines.
非弹性碰撞以及通过中间碰撞复合物的形成和随后衰变进行的基本化学反应，伴随着势能面上的一个相关深阱，这对精确的全量子力学方法（如密耦方法）构成了挑战。在本研究中，我们使用统计量子方法报告了这些复杂模式过程的温度相关态态速率系数的理论预测。这种统计绝热通道模型通过与文献中针对天体化学和天体物理学中一些感兴趣的系统（H + H、HD + H、SH + H和CH + H）的精确速率系数进行直接比较来进行基准测试。对于所有考虑的系统，至少在主导跃迁和低温下，发现误差小于2倍，这对于上述学科的应用来说足够精确。
