Hydrogen Abstraction Reactions of OH Radicals with CH3CH2CH2Cl and CH3CHClCH3: A Mechanistic and Kinetic Study
文献类型：期刊论文
| 作者 | Wang, Li1; Li, Yanjie1; He, Hongqing2 ; Zhang, Jinglai1
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| 刊名 | JOURNAL OF COMPUTATIONAL CHEMISTRY
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| 出版日期 | 2012-01-05 |
| 卷号 | 33期号:1页码:66-75 |
| 关键词 | CH3CH2CH2Cl CH3CHClCH3 Rate constants Direct dynamics method Four-parameter expression |
| 英文摘要 | The hydrogen abstraction reactions of OH radicals with CH3CH2CH2Cl (R1) and CH3CHClCH3 (R2) have been investigated theoretically by a dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points are calculated at the B3LYP/6-311G(d,p) level. To improve the reaction enthalpy and potential barrier of each reaction channel, the single point energy calculation is performed by the BMC-CCSD method. Using canonical variational transition-state theory (CVT) with the small-curvature tunneling correction, the rate constants are evaluated over a wide temperature range of 200-2000 K at the BMC-CCSD//B3LYP/6-311G(d,p) level. For the reaction channels with the negative barrier heights, the rate constants are calculated by using the CVT. The calculated total rate constants are consistent with available experimental data. The results show that at lower temperatures, the tunneling correction has an important contribution in the calculation of rate constants for all the reaction channels with the positive barrier heights, while the variational effect is found negligible for some reaction channels. For reactions OH radicals with CH3CH2CH2Cl (R1) and CH3CHClCH3 (R2), the channels of H-abstraction from -CH2- and -CHCl groups are the major reaction channels, respectively, at lower temperatures. With temperature increasing, contributions from other channels should be taken into account. Finally, the total rate constants are fitted by two models, i.e., three-parameter and four-parameter expressions. The enthalpies of formation of the species CH3CHClCH2, CH3CHCH2Cl, and CH2CH2CH2Cl are evaluated by isodesmic reactions. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 33: 66-75, 2012 |
| 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 ; THERMOCHEMICAL KINETICS ; DISSOCIATION-ENERGY ; ORGANIC-COMPOUNDS ; DENSITY ; 1-CHLOROPROPANE ; HYDROXYL ; DYNAMICS ; ENTHALPY |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000297852200008 |
| 公开日期 | 2015-07-14 |
| 版本 | 出版稿 |
| 源URL | [http://ir.wipm.ac.cn/handle/112942/1591]  |
| 专题 | 武汉物理与数学研究所_理论与交叉研究部 |
| 作者单位 | 1.Henan Univ, Inst Environm & Analyt Sci, Coll Chem & Chem Engn, Kaifeng 475004, Henan, Peoples R China 2.Chinese Acad Sci, Wuhan Ctr Magnet Resonance, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan Inst Phys & Math, Wuhan 430071, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wang, Li,Li, Yanjie,He, Hongqing,et al. Hydrogen Abstraction Reactions of OH Radicals with CH3CH2CH2Cl and CH3CHClCH3: A Mechanistic and Kinetic Study[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY,2012,33(1):66-75. |
| APA | Wang, Li,Li, Yanjie,He, Hongqing,&Zhang, Jinglai.(2012).Hydrogen Abstraction Reactions of OH Radicals with CH3CH2CH2Cl and CH3CHClCH3: A Mechanistic and Kinetic Study.JOURNAL OF COMPUTATIONAL CHEMISTRY,33(1),66-75. |
| MLA | Wang, Li,et al."Hydrogen Abstraction Reactions of OH Radicals with CH3CH2CH2Cl and CH3CHClCH3: A Mechanistic and Kinetic Study".JOURNAL OF COMPUTATIONAL CHEMISTRY 33.1(2012):66-75. |
入库方式： OAI收割
来源：武汉物理与数学研究所
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