O₂ 与 HOCO 反应的量子分子动力学研究

Quantum molecular dynamics study of the reaction of O2 with HOCO.

作者信息

Yu Hua-Gen, Muckerman James T

机构信息

Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973-5000, USA.

出版信息

J Phys Chem A. 2006 Apr 27;110(16):5312-6. doi: 10.1021/jp055623j.

DOI:10.1021/jp055623j

PMID:16623457

Abstract

The reaction of O2 with HOCO has been studied by using an ab initio direct dynamics method based on the UB3PW91 density functional theory. Results show that the reaction can occur via two mechanisms: direct hydrogen abstraction and an addition reaction through a short-lived HOC(O)O2 intermediate. The lifetime of the intermediate is predicted to be 660 +/- 30 fs. Although it is an activated reaction, the activation energy is only 0.71 kcal/mol. At room temperature, the obtained thermal rate coefficient is 2.1 x 10(-12) cm3 molecule(-1) s(-1), which is in good agreement with the experimental results.

摘要

利用基于UB3PW91密度泛函理论的从头算直接动力学方法研究了O2与HOCO的反应。结果表明，该反应可通过两种机制发生：直接氢提取和通过短寿命的HOC(O)O2中间体的加成反应。中间体的寿命预计为660±30飞秒。尽管这是一个活化反应，但活化能仅为0.71千卡/摩尔。在室温下，得到的热速率系数为2.1×10(-12)立方厘米·分子(-1)·秒(-1)，与实验结果吻合良好。