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。
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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
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.
期刊最新文献
Rate Constants of the H + HCF3 → H2 + CF3 Reaction from Ring Polymer Molecular Dynamics on a Highly Accurate Potential Energy Surface. Prediction of the Infrared Absorbance Intensities and Frequencies of Hydrocarbons: A Message Passing Neural Network Approach. N-Carbazolyl π-Radical and Its Antiaromatic Nitrenium Ion: A Threshold Photoelectron Spectroscopic Study. Effect of Fluorine Substitution on Magnetizabilities: Insights from Density Functional Theory and Benchmark Coupled-Cluster Calculations. Multireference Fock Space Coupled-Cluster Method for the (3,0) Sector.
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