Breakdown of the vibrationally adiabatic approximation in the early-barrier CH3 + HBr -> CH4 + Br reaction
文献类型：期刊论文
| 作者 | Song, Hongwei2; Ping, Leilei1,2; Wang, Yan2,3; Yang, Minghui2 |
| 刊名 | THEORETICAL CHEMISTRY ACCOUNTS
 |
| 出版日期 | 2017-04-17 |
| 卷号 | 136期号:5 |
| 关键词 | Quantum Dynamics Quasi-classical Trajectory Polyatomic Reaction Vibrationally Adiabatic Approximation |
| DOI | 10.1007/s00214-017-2089-8 |
| 文献子类 | Article |
| 英文摘要 | The prototypical hydrogen abstraction reaction between hydrogen bromide and methyl was investigated using both the eight-dimensional quantum dynamics and quasi-classical trajectory methods. The dynamics calculations showed that the individual excitation of the CH3 symmetric stretching mode, the umbrella mode and the HBr stretching mode visibly enhances the reaction while they are all less efficient than the translational energy in promoting the reaction, as expected for an early-barrier reaction. The vibrationally adiabatic approximation fails in predicting the promotional effect of the excitation energy in the CH3 umbrella mode. However, the promotional effect can be partially rationalized by the sudden vector projection model as there exists non-negligible coupling between the vector of the CH3 umbrella mode and the reaction coordinate vector at the transition state. |
| WOS关键词 | HYDROGEN ABSTRACTION REACTION ; NEGATIVE ACTIVATION-ENERGIES ; ABSOLUTE RATE CONSTANTS ; REACTION DYNAMICS ; QUANTUM DYNAMICS ; AB-INITIO ; TRANSITION-STATE ; BIMOLECULAR REACTIONS ; METATHESIS REACTIONS ; REACTIVE SCATTERING |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000404248300001 |
| 资助机构 | National Natural Science Foundation of China(21603266 ; National Natural Science Foundation of China(21603266 ; 21373266) ; 21373266) ; National Natural Science Foundation of China(21603266 ; National Natural Science Foundation of China(21603266 ; 21373266) ; 21373266) |
| 源URL | [http://ir.wipm.ac.cn/handle/112942/11470]  |
| 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.Huazhong Normal Univ, Coll Phys Sci & Technol, Wuhan 430079, Peoples R China 2.Chinese Acad Sci, Key Lab Magnet Resonance Biol Syst, State Key Lab Magnet Resonance & Atom & Mol Phys, Natl Ctr Magnet Resonance Wuhan,Wuhan Inst Phys &, Wuhan 430071, Peoples R China 3.Hubei Univ Nationalities, Sch Chem & Environm Engn, Enshi 445000, Peoples R China |
| 推荐引用方式 GB/T 7714 | Song, Hongwei,Ping, Leilei,Wang, Yan,et al. Breakdown of the vibrationally adiabatic approximation in the early-barrier CH3 + HBr -> CH4 + Br reaction[J]. THEORETICAL CHEMISTRY ACCOUNTS,2017,136(5). |
| APA | Song, Hongwei,Ping, Leilei,Wang, Yan,&Yang, Minghui.(2017).Breakdown of the vibrationally adiabatic approximation in the early-barrier CH3 + HBr -> CH4 + Br reaction.THEORETICAL CHEMISTRY ACCOUNTS,136(5). |
| MLA | Song, Hongwei,et al."Breakdown of the vibrationally adiabatic approximation in the early-barrier CH3 + HBr -> CH4 + Br reaction".THEORETICAL CHEMISTRY ACCOUNTS 136.5(2017). |
入库方式： OAI收割
来源：武汉物理与数学研究所
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