Department of Physics, Firat University, 23169 Elazig, Turkey.
J Phys Chem A. 2012 Jan 12;116(1):132-8. doi: 10.1021/jp210254t. Epub 2011 Dec 15.
The dynamics and kinetics of the Li + H₂⁺ reaction and its isotopic variants (D₂⁺ and T₂⁺) have been studied by using a time-dependent wave packet (TDWP) coupled-channel (CC) method on the ab initio potential energy surface (PES) of Martinazzo et al. [J. Chem. Phys. 2003, 119, 21]. Total initial v = 0, j = 0 state-selected reaction probabilities for the Li + H₂⁺ reaction and its isotopic variants have been calculated from the threshold up to 1 eV for total angular momenta J from 0 to 90. Integral cross sections have been evaluated from the reaction probabilities at collision energies from threshold (≈0.2 eV) up to 1.0 eV collision. The calculated rate constants as a function of temperature show an Arrhenius type behavior in the 200 ≤ T ≤ 1000 K temperature interval. It has been found to be a considerable large intermolecular kinetic isotope effect. The TDWP-CC results are in overall good agreement with those obtained applying the TDWP Centrifugal-Sudden (CS) approximation, showing that the CS approximation is rather accurate for the title reaction.
利用 Martinazzo 等人的从头算势能面（PES）上的含时波包（TDWP）耦合通道（CC）方法，研究了 Li + H₂⁺反应及其同位素变体（D₂⁺和 T₂⁺）的动力学和反应动力学。计算了总初始 v = 0，j = 0 态选择的 Li + H₂⁺反应及其同位素变体的反应概率，从阈值到 1 eV，总角动量 J 从 0 到 90。从反应概率评估积分截面在从阈值（≈0.2 eV）到 1.0 eV 碰撞的碰撞能下。计算得到的速率常数随温度的变化表现出 200 ≤ T ≤ 1000 K 温度范围内的 Arrhenius 型行为。发现它是一个相当大的分子间动力学同位素效应。TDWP-CC 结果与应用 TDWP 离心-突发（CS）近似得到的结果总体上吻合良好，表明 CS 近似对于标题反应相当准确。
