Kinetics of the OH+HCl→H2 O+Cl reaction: Rate determining roles of stereodynamics and roaming and of quantum tunneling,Journal of Computational Chemistry

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Kinetics of the OH+HCl→H2 O+Cl reaction: Rate determining roles of stereodynamics and roaming and of quantum tunneling
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-10-26 , DOI: 10.1002/jcc.25597
Nayara D. Coutinho ₁ , Flavio O. Sanches‐Neto ₂ , Valter H. Carvalho‐Silva ₃ , Heibbe C. B. Oliveira ₁ , Luiz A. Ribeiro ₃ , Vincenzo Aquilanti _{4,

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Affiliation

The OH + HCl → H2O + Cl reaction is one of the most studied four‐body systems, extensively investigated by both experimental and theoretical approaches. Here, as a continuation of our previous work on the OH + HBr and OH + HI reactions, which manifest an anti‐Arrhenius behavior that was explained by stereodynamic and roaming effects, we extend the strategy to understand the transition to the sub‐Arrhenius behavior occurring for the HCl case. As previously, we perform first‐principles on‐the‐fly Born–Oppenheimer molecular dynamics calculations, thermalized at four temperatures (50, 200, 350, and 500 K), but this time we also apply a high‐level transition‐state‐theory, modified to account for tunneling conditions. We find that the theoretical rate constants calculated with Bell tunneling corrections are in good agreement with extensive experimental data available for this reaction in the ample temperature range: (i) simulations show that the roles of molecular orientation in promoting this reaction and of roaming in finding the favorable path are minor than in the HBr and HI cases, and (ii) dominating is the effect of quantum mechanical penetration through the energy barrier along the reaction path on the potential energy surface. The discussion of these results provides clarification of the origin on different non‐Arrhenius mechanisms observed along this series of reactions. © 2018 Wiley Periodicals, Inc.

中文翻译：

OH+HCl→H2 O+Cl 反应的动力学：立体动力学和漫游以及量子隧穿的速率决定作用

OH + HCl → H2O + Cl 反应是研究最多的四体系统之一，通过实验和理论方法进行了广泛研究。在这里，作为我们之前关于 OH + HBr 和 OH + HI 反应的工作的延续，它们表现出通过立体动力学和漫游效应解释的反阿伦尼乌斯行为，我们扩展了策略以了解向亚阿伦尼乌斯行为的转变发生在 HCl 的情况下。和以前一样，我们在四个温度（50、200、350 和 500 K）下进行了第一性原理的动态波恩-奥本海默分子动力学计算，但这次我们也应用了高级过渡态-理论，修改以考虑隧道条件。我们发现用贝尔隧穿校正计算的理论速率常数与在充足的温度范围内可用于该反应的大量实验数据非常一致：（i）模拟表明分子取向在促进该反应中的作用和漫游在寻找有利的路径比 HBr 和 HI 的情况要小，并且（ii）占主导地位的是量子力学穿透势能表面上沿反应路径的能垒的影响。对这些结果的讨论澄清了在这一系列反应中观察到的不同非阿伦尼乌斯机制的起源。© 2018 Wiley Periodicals, Inc. (i) 模拟表明，分子取向在促进该反应中的作用和漫游在寻找有利路径中的作用比 HBr 和 HI 情况下要小，并且 (ii) 占主导地位的是量子力学穿透沿能量势垒的影响势能面上的反应路径。对这些结果的讨论澄清了在这一系列反应中观察到的不同非阿伦尼乌斯机制的起源。© 2018 Wiley Periodicals, Inc. (i) 模拟表明，分子取向在促进该反应中的作用和漫游在寻找有利路径中的作用比 HBr 和 HI 情况下要小，并且 (ii) 占主导地位的是量子力学穿透沿能量势垒的影响势能面上的反应路径。对这些结果的讨论澄清了在这一系列反应中观察到的不同非阿伦尼乌斯机制的起源。© 2018 Wiley Periodicals, Inc. 对这些结果的讨论澄清了在这一系列反应中观察到的不同非阿伦尼乌斯机制的起源。© 2018 Wiley Periodicals, Inc. 对这些结果的讨论澄清了在这一系列反应中观察到的不同非阿伦尼乌斯机制的起源。© 2018 Wiley Periodicals, Inc.

更新日期：2018-10-26

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