Morita Masato, Zuo Junxiang, Guo Hua, Balakrishnan Naduvalath
Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, Las Vegas, Nevada 89154, USA.
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
J Chem Phys. 2021 Mar 14;154(10):104304. doi: 10.1063/5.0043658.
We examine rotational transitions of HCl in collisions with H by carrying out quantum mechanical close-coupling and quasi-classical trajectory (QCT) calculations on a recently developed globally accurate full-dimensional ab initio potential energy surface for the HCl system. Signatures of rainbow scattering in rotationally inelastic collisions are found in the state resolved integral and differential cross sections as functions of the impact parameter (initial orbital angular momentum) and final rotational quantum number. We show the coexistence of distinct dynamical regimes for the HCl rotational transition driven by the short-range repulsive and long-range attractive forces whose relative importance depends on the collision energy and final rotational state, suggesting that the classification of rainbow scattering into rotational and l-type rainbows is effective for H + HCl collisions. While the QCT method satisfactorily predicts the overall behavior of the rotationally inelastic cross sections, its capability to accurately describe signatures of rainbow scattering appears to be limited for the present system.
我们通过在最近为HCl系统开发的全局精确全维从头算势能面上进行量子力学紧密耦合和准经典轨迹（QCT）计算，研究了HCl与H碰撞中的转动跃迁。在转动非弹性碰撞中，彩虹散射的特征出现在状态分辨的积分和微分截面中，这些截面是碰撞参数（初始轨道角动量）和最终转动量子数的函数。我们展示了由短程排斥力和长程吸引力驱动的HCl转动跃迁中不同动力学区域的共存，其相对重要性取决于碰撞能量和最终转动状态，这表明将彩虹散射分为转动彩虹和l型彩虹对H + HCl碰撞是有效的。虽然QCT方法令人满意地预测了转动非弹性截面的整体行为，但对于当前系统，其准确描述彩虹散射特征的能力似乎有限。
