CF3CH2CH3+OH的反应机理及动力学性质的理论研究

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (6): 1240.

CF₃CH₂CH₃+OH的反应机理及动力学性质的理论研究

王永霞, 高红, 王钦, 刘靖尧

吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023

收稿日期:2009-10-10 出版日期:2010-06-10 发布日期:2010-06-10
通讯作者: 刘靖尧, 女, 博士, 教授, 博士生导师, 主要从事小分子反应动力学研究. E-mail: ljy121@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 20333050, 20303007, 20973077)和教育部新世纪优秀人才支持计划(NCET)资助.

Theoretical Study on the Mechanism and Dynamic of CF₃CH₂CH₃ Reaction with OH Radicals

WANG Yong-Xia, GAO Hong, WANG Qin, LIU Jing-Yao*

State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Received:2009-10-10 Online:2010-06-10 Published:2010-06-10
Contact: LIU Jing-Yao. E-mail: ljy121@jlu.edu.cn
Supported by:
国家自然科学基金(批准号: 20333050, 20303007, 20973077)和教育部新世纪优秀人才支持计划(NCET)资助.

摘要/Abstract

摘要：

采用密度泛函理论BB1K/6-31+G(d,p)计算了反应CF₃CH₂CH₃+OH各反应通道上驻点的稳定结构和振动频率, 并分别在BMC-CCSD, MC-QCISD和G3(MP2)水平上进行了单点能校正. 运用变分过渡态理论, 在BMC-CCSD//BB1K, MC-QCISD//BB1K, G3(MP2)//BB1K以及BB1K水平上计算了各反应通道的速率常数, 讨论了—CH₂和—CH₃基团上H提取通道对总反应的贡献, 并与已有实验和理论结果进行了对比. 计算结果表明, BMC-CCSD水平上的速率常数与实验测量值符合得很好, 进而给出了该水平上反应在200~1000 K温度范围内速率常数k(cm³?molecule^-1?s^-1)的三参数表达式: k=1.90×10^-21T^3.21exp(-292.62/T).

关键词: 直接动力学; 速率常数; 变分过渡态理论; CF3CH2CH3

Abstract:

The optimized geometries and frequencies of all the stationary points involved in each reaction channel of the CF₃CH₂CH₃+OH reaction were calculated at the BB1K/6-31+G(d,p) level, and the potential energy profile is further refined by single-point energy calculations at the BMC-CCSD, MC-QCISD and G3(MP2) levels. The rate constants of all channels were evaluated by variational transition state theory(VTST) at the BMC-CCSD//BB1K, MC-QCISD//BB1K, G3(MP2)//BB1K and BB1K levels over a wide temperature range of 200—1000 K, and the contribution of H-abstraction from the —CH₂ and —CH₃ groups to the total reaction was discussed. The present calculations show that the rate constants evaluated at the BMC-CCSD//BB1K level are in excellent agreement with the available experimental values in the measured tempe-rature range. Finally, the three-parameter rate-temperature expression of the total reaction over the whole temperature range 200—1000 K was given as k=1.90×10^-21T^3.21exp(-292.62/T).

Key words: Direct dynamics; Rate constant; Variational transition-state theory; CF3CH2CH3

TrendMD:

王永霞, 高红, 王钦, 刘靖尧. CF₃CH₂CH₃+OH的反应机理及动力学性质的理论研究. 高等学校化学学报, 2010, 31(6): 1240.

WANG Yong-Xia, GAO Hong, WANG Qin, LIU Jing-Yao*. Theoretical Study on the Mechanism and Dynamic of CF₃CH₂CH₃ Reaction with OH Radicals. Chem. J. Chinese Universities, 2010, 31(6): 1240.

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CF₃CH₂CH₃+OH的反应机理及动力学性质的理论研究

Theoretical Study on the Mechanism and Dynamic of CF₃CH₂CH₃ Reaction with OH Radicals

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