A new ground electronic state potential energy surface of HeLiH+: Analytical representation and investigation of the dynamics of He + LiH+ (v = 0, j = 0) → LiHe+ + H reaction.
Ajay Mohan Singh Rawat, Mohammed Alamgir, Sugata Goswami, Susanta Mahapatra
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引用次数: 0
Abstract
An improved global potential energy surface (PES) for the electronic ground state of the HeLiH+ system is reported. The data points are calculated at the full configuration-interaction level of theory and extrapolated to the complete basis set limit. The fitting procedure implements a combination of neural network and Aguado-Paniagua functional forms to fit the ab initio data points. The fitted surface reproduces the ab initio data points accurately in short as well as long ranges and has an overall root mean square error of 1.76 × 10-3 eV (14.21 cm-1) in energy space <10 and 9.28 × 10-4 eV (7.48 cm-1) upto 2 eV. The optimized global minimum is also accurately reproduced using the fitted surface. To establish the accuracy of the new PES, dynamics investigation of the He + LiH+(v = 0, j = 0) → LiHe+ + H reaction is performed using the Coriolis coupled quantum mechanical and quasi-classical trajectory methods. The results, such as integral cross sections and rate constants, show the effect of the opening of the collision-induced dissociation (CID) channel at low collision energy and are significantly different from the earlier study of Tacconi et al. [Phys. Chem. Chem. Phys. 14, 637-645 (2012)]. These discrepancies appear to be a result of the treatment of the CID channel in the dynamics calculations, which is excluded from the reactive channel in the current work.
HeLiH+ 的新基态电子势能面:He + LiH+ (v = 0, j = 0) → LiHe+ + H 反应动力学的分析表示和研究。
报告了 HeLiH+ 系统电子基态的改进型全局势能面 (PES)。数据点是在全构型-相互作用理论水平上计算的,并推断至完整基集极限。拟合过程结合了神经网络和阿瓜多-帕尼亚瓜函数形式来拟合 ab initio 数据点。拟合表面在短程和长程上都准确地再现了 ab initio 数据点,在能量空间中的总体均方根误差为 1.76 × 10-3 eV(14.21 cm-1)。
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