Full-dimensional coupled-channel statistical approach to atom-triatom systems and applications to H/D + O3 reaction,Journal of Computational Chemistry

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Full-dimensional coupled-channel statistical approach to atom-triatom systems and applications to H/D + O3 reaction
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2024-09-02 , DOI: 10.1002/jcc.27500
Dongzheng Yang ₁ , Hua Guo ₁

Affiliation

The statistical quantum model (SQM), which assumes that the reactivity is controlled by entrance/exit channel quantum capture probabilities, is well suited for chemical reactions with a long-lived intermediate complex. In this work, a time-independent coupled-channel implementation of the SQM approach is developed for atom-triatom systems in full dimensionality. As SQM treats the capture dynamics quantum mechanically, it is capable of handling quantum effects such as tunneling. A detailed study of the H/D + O₃ capture dynamics was performed by applying the newly developed SQM method on an accurate global potential energy surface. Agreement with previous ring polymer molecular dynamics (RPMD) results on the same potential energy surface is excellent except for very low temperatures. The SQM results are also in reasonably good agreement with available experimental rate coefficients. The strong H/D kinetic isotope effect underscores the dominant role of quantum tunneling under an entrance channel barrier at low temperatures.

中文翻译：

原子-硅旋蝇体系的全维耦合通道统计方法及其在 H/D + O3 反应中的应用

统计量子模型（SQM）假设反应性由进入/出口通道量子捕获概率控制，非常适合与长寿命中间复合物发生化学反应。在这项工作中，为全维原子-三原子系统开发了 SQM 方法的时间无关耦合通道实现。由于 SQM 以机械方式处理捕获动力学量子，因此它能够处理量子效应，例如隧穿。通过在精确的全球势能表面上应用新开发的 SQM 方法，对 H/D + O₃ 捕获动力学进行了详细研究。除极低温度外，在相同势能表面上与先前的环状聚合物分子动力学（RPMD）结果的一致性非常好。SQM 结果也与可用的实验速率系数相当吻合。强大的 H/D 动力学同位素效应强调了低温下入口通道势垒下量子隧穿的主导作用。

更新日期：2024-09-02

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