物理化学学报2011，Vol.27Issue(2)：337-342,6.
CH3OCF2CF2OCH3+Cl的反应机理及动力学性质
Mechanism and Kinetics of the CH3OCF2CF2OCH3+Cl Reaction
摘要
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 (kT) 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 kT(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: kT=0.40×10-14T1.05exp(-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分类
化学化工引用本文复制引用
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(2):337-342,6.基金项目
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 （20333050,20303007,20973077）
