| CF3CH2CH3+OH的反应机理及动力学性质的理论研究 |
| |
| 引用本文： | 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[J].高等学校化学学报,2010,31(6):1240. |
| |
| 作者姓名： | 王永霞 高红 王钦 刘靖尧 |
| |
| 作者单位： | 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 |
| |
| 基金项目： | 国家自然科学基金，教育部新世纪优秀人才支持计划 |
| |
| 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=1.90×10-21T3.21exp(-292.62/T).
|
| 关 键 词： | 直接动力学 速率常数 变分过渡态理论 CF3CH2CH3 |
| 收稿时间： | 2009-10-10 |
Theoretical Study on the Mechanism and Dynamic of CF_3CH_2CH_3 Reaction with OH Radicals |
| |
| WANG Yong-Xia,GAO Hong,WANG Qin,LIU Jing-Yao.Theoretical Study on the Mechanism and Dynamic of CF_3CH_2CH_3 Reaction with OH Radicals[J].Chemical Research In Chinese Universities,2010,31(6):1240. |
| |
| Authors: | WANG Yong-Xia GAO Hong WANG Qin LIU Jing-Yao |
| |
| Institution: | State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China |
| |
| 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 200100... |
| |
| Keywords: | CF3CH2CH3 |
| 本文献已被 CNKI 万方数据 等数据库收录！ |
| 点击此处可从《高等学校化学学报》浏览原始摘要信息 |
| 点击此处可从《高等学校化学学报》下载免费的PDF全文 |
|
