Unke Oliver T, Castro-Palacio Juan Carlos, Bemish Raymond J, Meuwly Markus
Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland.
Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117, USA.
J Chem Phys. 2016 Jun 14;144(22):224307. doi: 10.1063/1.4951697.
The collisional dynamics of N2 (+)((2)Σg (+)) cations with Ar atoms is studied using quasi-classical simulations. N2 (+)-Ar is a proxy to study cooling of molecular ions and interesting in its own right for molecule-to-atom charge transfer reactions. An accurate potential energy surface (PES) is constructed from a reproducing kernel Hilbert space (RKHS) interpolation based on high-level ab initio data. The global PES including the asymptotics is fully treated within the realm of RKHS. From several ten thousand trajectories, the final state distribution of the rotational quantum number of N2 (+) after collision with Ar is determined. Contrary to the interpretation of previous experiments which indicate that up to 98% of collisions are elastic and conserve the quantum state, the present simulations find a considerably larger number of inelastic collisions which supports more recent findings.
利用准经典模拟研究了N2(+)((2)Σg(+))阳离子与Ar原子的碰撞动力学。N2(+)-Ar是研究分子离子冷却的一个替代体系，其本身对于分子到原子的电荷转移反应也很有趣。基于高水平的从头算数据，通过再生核希尔伯特空间（RKHS）插值构建了精确的势能面（PES）。包括渐近线在内的全局PES在RKHS领域内得到了充分处理。从数万条轨迹中，确定了N2(+)与Ar碰撞后转动量子数的最终态分布。与先前实验的解释相反，先前实验表明高达98%的碰撞是弹性的且保持量子态，而目前的模拟发现了大量非弹性碰撞，这支持了更多近期的研究结果。
