Theoretical study of the reactions CF3CH2OCHF2+OH/Cl and its product radicals and parent ether (CH3CH2OCH3) with OH
文献类型：期刊论文
| 作者 | Yang, Lei1; Liu, Jing-Yao1; Wang, Li1; He, Hong-Qing1,2 ; Wang, Ying1; Li, Ze-Sheng1
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| 刊名 | JOURNAL OF COMPUTATIONAL CHEMISTRY
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| 出版日期 | 2008-03-01 |
| 卷号 | 29期号:4页码:550-561 |
| 关键词 | density functional theory direct dynamics rate constant variational transition-state theory |
| 英文摘要 | A dual-level direct dynamic method is employed to study the reaction mechanisms of CF3CH2OCHF2 (HFE-245fa2; HFE-245mf) with the OH radicals and Cl atoms. Two hydrogen abstraction channels and two displacement processes are found for each reaction. For further study, the reaction mechanisms of its products (CF3CH2OCF2 and CF3CHOCHF2) and parent ether CH3CH2OCH3 with OH radical are investigated theoretically. The geometries and frequencies of all the stationary points and the minimum energy paths (MEPs) are calculated at the B3LYP/6-311G(d,p) level. The energetic information along the MEPs is further refined at the G3(MP2) level of theory. For reactions CF3CH2OCHF2 + OH/Cl, the calculation indicates that the hydrogen abstraction from -CH2- group is the dominant reaction channel, and the displacement processes may be negligible because of the high barriers. The standard enthalpies of formation for the reactant CF3CH2OCHF2, and two products CF3CH2OCF2 and CF3CHOCHF2 are evaluated via group-balanced isodesmic reactions. The rate constants of reactions CF3CH2OCHF2 + OH/Cl and CH3CH2OCH3 + OH are estimated by using the variational transition state theory over a wide range of temperature (200-2000 K). The agreement between the theoretical and experimental rate constants is good in the measured temperature range. From the comparison between the rate constants of the reactions CF3CH2OCHF2 and CH3CH2OCH3 with OH, it is shown that the fluorine substitution decreases the reactivity of the C-H bond. (c) 2007 Wiley Periodicals, Inc. |
| WOS标题词 | Science & Technology ; Physical Sciences |
| 类目[WOS] | Chemistry, Multidisciplinary |
| 研究领域[WOS] | Chemistry |
| 关键词[WOS] | TRANSITION-STATE THEORY ; RATE CONSTANTS ; CL ATOMS ; ATMOSPHERIC CHEMISTRY ; CHLORINE ATOMS ; ARRHENIUS PARAMETERS ; FLUORINATED ETHERS ; HYDROFLUOROETHERS ; CF3CHCLOCHF2 ; DENSITY |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000253648500006 |
| 版本 | 出版稿 |
| 源URL | [http://ir.wipm.ac.cn/handle/112942/8066]  |
| 专题 | 武汉物理与数学研究所_2011年以前论文发表（包括2011年） |
| 作者单位 | 1.Jilin Univ, Inst Theoret Chem, State Key Lab Theoret & Computat Chem, Changchun 130023, Peoples R China 2.Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan 430071, Peoples R China |
| 推荐引用方式 GB/T 7714 | Yang, Lei,Liu, Jing-Yao,Wang, Li,et al. Theoretical study of the reactions CF3CH2OCHF2+OH/Cl and its product radicals and parent ether (CH3CH2OCH3) with OH[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY,2008,29(4):550-561. |
| APA | Yang, Lei,Liu, Jing-Yao,Wang, Li,He, Hong-Qing,Wang, Ying,&Li, Ze-Sheng.(2008).Theoretical study of the reactions CF3CH2OCHF2+OH/Cl and its product radicals and parent ether (CH3CH2OCH3) with OH.JOURNAL OF COMPUTATIONAL CHEMISTRY,29(4),550-561. |
| MLA | Yang, Lei,et al."Theoretical study of the reactions CF3CH2OCHF2+OH/Cl and its product radicals and parent ether (CH3CH2OCH3) with OH".JOURNAL OF COMPUTATIONAL CHEMISTRY 29.4(2008):550-561. |
入库方式： OAI收割
来源：武汉物理与数学研究所
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