CH3OCF2CF2OCH3+Cl的反应机理及动力学性质

doi:10.3866/PKU.WHXB20110201

物理化学学报 >> 2011, Vol. 27 >> Issue (02): 337-342.doi: 10.3866/PKU.WHXB20110201

CH₃OCF₂CF₂OCH₃+Cl的反应机理及动力学性质

崔凤超, 于洪波, 王钦, 叶宛丽, 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:2010-09-27 修回日期:2010-11-12 发布日期:2011-01-25
通讯作者: 刘靖尧 E-mail:ljy121@jlu.edu.cn
基金资助:
国家自然科学基金(20333050, 20303007, 20973077)和教育部新世纪优秀人才支持计划(NCET)资助项目

Mechanism and Kinetics of the CH₃OCF₂CF₂OCH₃+Cl Reaction

CUI Feng-Chao, YU Hong-Bo, WANG Qin, YE Wan-Li, LIU Jing-Yao

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

Received:2010-09-27 Revised:2010-11-12 Published:2011-01-25
Contact: LIU Jing-Yao E-mail:ljy121@jlu.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (20333050, 20303007, 20973077) and Program for New Century Excellent Talents in University, China (NCET).

摘要/Abstract

摘要：

利用密度泛函理论直接动力学方法研究了反应CH₃OCF₂CF₂OCH₃+Cl的微观机理和动力学性质. 在BB1K/6-31+G(d,p)水平上获得了反应的势能面信息, 计算中考虑了反应物CH₃OCF₂CF₂OCH₃两个稳定构象(SC1和SC2)的氢提取通道和取代反应通道. 利用改进的正则变分过渡态理论结合小曲率隧道效应(ICVT/SCT)计算了各氢提取通道的速率常数, 进而根据Boltzmann配分函数得到总包反应速率常数(k_T)以及每个构象对总反应的贡献. 结果表明296 K温度下计算的k_T(ICVT/SCT)值与已有实验值符合得很好. 由于缺乏其他温度速率常数的实验数据, 我们预测了该反应在200-2000 K温度区间内反应速率常数的三参数表达式: k_T=0.40×10^-14T^1.05exp(-206.16/T).

关键词: 密度泛函理论, 直接动力学, 速率常数, 改进的正则变分过渡态理论, CH₃OCF₂CF₂OCH₃

Abstract:

A direct density functional theory dynamics method was used to determine the mechanism and kinetics of the CH₃OCF₂CF₂OCH₃+Cl reaction. Potential energy surface information was obtained at the BB1K/6-31+G(d,p) level. The hydrogen abstraction channels and displacement processes of the two stable conformers (SC1 and SC2) of CH₃OCF₂CF₂OCH₃ were taken into consideration. Theoretical rate constants of the individual H-abstraction channels (one from SC1 and two from SC2) were calculated by improved canonical variational transition state theory (ICVT) with a small-curvature tunneling (SCT) correction. The overall rate constant (k_T) was obtained by considering the weight factor of each conformer from the Boltzmann distribution function and the contribution of the two conformers to the whole reaction was discussed. The calculated k_T(ICVT/SCT) at 296 K agrees well with the experimental value. Since experimental data were lacking for other temperatures, a three-parameter rate constant temperature expression for the total reaction within 200-2000 K was fitted to: k_T=0.40×10^-14T^1.05exp(-206.16/T).

Key words: Density functional theory, Direct dynamics, Rate constant, Improved canonical variational transition state theory, CH₃OCF₂CF₂OCH₃

崔凤超, 于洪波, 王钦, 叶宛丽, 刘靖尧. CH₃OCF₂CF₂OCH₃+Cl的反应机理及动力学性质[J]. 物理化学学报, 2011, 27(02), 337-342. doi: 10.3866/PKU.WHXB20110201

CUI Feng-Chao, YU Hong-Bo, WANG Qin, YE Wan-Li, LIU Jing-Yao. Mechanism and Kinetics of the CH₃OCF₂CF₂OCH₃+Cl Reaction[J]. Acta Phys. -Chim. Sin. 2011, 27(02), 337-342. doi: 10.3866/PKU.WHXB20110201

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB20110201

https://www.whxb.pku.edu.cn/CN/Y2011/V27/I02/337

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CH₃OCF₂CF₂OCH₃+Cl的反应机理及动力学性质

Mechanism and Kinetics of the CH₃OCF₂CF₂OCH₃+Cl Reaction

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