高精度势能面上环状聚合物分子动力学得出的 H + HCF3 → H2 + CF3 反应速率常数。

IF 2.7 2区化学 Q3 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry A Pub Date : 2024-10-29 DOI:10.1021/acs.jpca.4c05352

Yongfa Zhu, Hongwei Song

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引用次数: 0

摘要

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。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Rate Constants of the H + HCF₃ → H₂ + CF₃ Reaction from Ring Polymer Molecular Dynamics on a Highly Accurate Potential Energy Surface.

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.

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来源期刊

The Journal of Physical Chemistry A 化学-物理：原子、分子和化学物理

CiteScore

5.20

自引率

10.30%

发文量

922

审稿时长

1.3 months

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.