Department of Physics, Stockholm University, Albanova University Center, S-106 91 Stockholm, Sweden.
Department of Chemical Engineering, University of California, Davis, Davis, California 95616, USA.
J Chem Phys. 2019 Dec 7;151(21):214305. doi: 10.1063/1.5128357.
The cross section and final state distribution for mutual neutralization in collisions of H with Cl have been calculated using an ab initio quantum mechanical approach. It is based on potential energy curves and nonadiabatic coupling elements for the six lowest Σ states of HCl computed with the multireference configuration interaction method. The reaction is found to be driven by nonadiabatic interactions occurring at relatively small internuclear distances (R < 6 a). Effects on the mutual neutralization cross section with respect to the asymptotic form of the potential energy curves, inclusion of closed channels, as well as isotopic substitution are investigated. The effect of spin-orbit interaction is investigated using a semiempirical model and found to be small. A simple two-state Landau-Zener calculation fails to predict the cross section.
使用从头算量子力学方法计算了 H 与 Cl 碰撞中相互中和的截面和末态分布。它基于多参考组态相互作用方法计算的 HCl 的六个最低Σ态的势能曲线和非绝热耦合元素。反应是由在相对较小的核间距（R < 6 a）处发生的非绝热相互作用驱动的。研究了势能曲线渐近形式、闭通道包含以及同位素取代对相互中和截面的影响。使用半经验模型研究了自旋轨道相互作用的影响，发现影响很小。简单的两态朗道-泽纳计算未能预测截面。
