Department of Chemistry, Indian Institute of Technology Guwahati , Guwahati 781039, India.
J Phys Chem A. 2013 Dec 12;117(49):13070-8. doi: 10.1021/jp408550c. Epub 2013 Dec 2.
An analytical potential energy surface (PES) for the ground state of the HeHNe system has been constructed from a set of 19,605 ab initio data points, obtained from coupled cluster singles and doubles with perturbative triples correction calculations and the aug-cc-pVQZ basis set. The PES is based on the many-body expansion form proposed by Aguado and Paniagua (J. Chem. Phys. 1992, 96, 1265), and it has a root-mean-square error of 0.03 kcal/mol. The minimum energy pathways (MEPs) for different Ne-H-He angles are calculated, and it is found that the MEP for 180° (linear) goes through the deepest potential energy well. Preliminary quantum dynamical studies are performed for the He + NeH(+) (v = 0-2, j = 0-3) → HeH(+) + Ne reaction in the 0.0-0.5 eV collision energy range. Quantum calculations are carried out using a time-dependent wave packet method within the centrifugal sudden approximation. Reaction probabilities exhibit strong oscillatory behavior arising because of the metastable HeHNe. Vibrational excitation has been found to enhance the reaction cross sections.
已构建了HeHNe体系基态的分析势能面（PES），该PES 是基于 Aguado 和 Paniagua（J. Chem. Phys. 1992, 96, 1265）提出的多体展开形式，使用了耦合簇单双加微扰三的计算和 aug-cc-pVQZ 基组，从 19605 个从头算数据点中获得。PES 的均方根误差为 0.03 kcal/mol。计算了不同 Ne-H-He 角度的最低能量途径（MEP），发现 180°（线性）的 MEP 通过最深的势能阱。在 0.0-0.5 eV 碰撞能范围内，对 He + NeH(+)（v = 0-2，j = 0-3）→HeH(+) + Ne 反应进行了初步的量子动力学研究。使用离心突发近似下的时变波包方法进行量子计算。由于亚稳HeHNe的存在，反应概率表现出强烈的振荡行为。振动激发已被发现可以提高反应截面。
