{"title":"Rate Constants of the H + HCF<sub>3</sub> → H<sub>2</sub> + CF<sub>3</sub> Reaction from Ring Polymer Molecular Dynamics on a Highly Accurate Potential Energy Surface.","authors":"Yongfa Zhu, Hongwei Song","doi":"10.1021/acs.jpca.4c05352","DOIUrl":null,"url":null,"abstract":"<p><p>The reaction between H and HCF<sub>3</sub> is the primary consumption pathway of HCF<sub>3</sub> in the atmosphere and combustion. In this work, ring polymer molecular dynamics (RPMD) calculations are performed to calculate the rate constants of the reaction on a recently developed accurate potential energy surface. 36, 20, and 8 beads are used to compute the rate constants at 350 K ≤ <i>T</i> < 800 K, 800 K ≤ <i>T</i> ≤ 1000 K, and <i>T</i> > 1000 K, respectively. The obtained RPMD rate constants agree well with the experimental measurements. In addition, a detailed analysis of the free-energy curves and transmission coefficients reveals that the quantum tunneling significantly affects the reaction dynamics, even at high temperatures.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"9606-9613"},"PeriodicalIF":2.7000,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.4c05352","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/29 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The reaction between H and HCF3 is the primary consumption pathway of HCF3 in the atmosphere and combustion. In this work, ring polymer molecular dynamics (RPMD) calculations are performed to calculate the rate constants of the reaction on a recently developed accurate potential energy surface. 36, 20, and 8 beads are used to compute the rate constants at 350 K ≤ T < 800 K, 800 K ≤ T ≤ 1000 K, and T > 1000 K, respectively. The obtained RPMD rate constants agree well with the experimental measurements. In addition, a detailed analysis of the free-energy curves and transmission coefficients reveals that the quantum tunneling significantly affects the reaction dynamics, even at high temperatures.
H 与 HCF3 之间的反应是大气和燃烧中 HCF3 的主要消耗途径。在这项工作中，通过环聚合物分子动力学（RPMD）计算，在最近开发的精确势能面上计算出了反应的速率常数。在 350 K ≤ T < 800 K、800 K ≤ T ≤ 1000 K 和 T > 1000 K 条件下，分别使用 36、20 和 8 个珠子计算速率常数。所得到的 RPMD 速率常数与实验测量结果非常吻合。此外，对自由能曲线和传输系数的详细分析显示，量子隧道对反应动力学有显著影响，即使在高温下也是如此。
期刊介绍：
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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