Kinetic isotope effect of the O-16+O-36(2) and O-18+O-32(2) isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study
文献类型：期刊论文
| 作者 | Sun, Zhigang1,2,3,4; Yu, Dequan1,2,3,4; Xie, Wenbo1,2,3,4; Hou, Jiayi1,2,3,4; Dawes, Richard5; Guo, Hua6 |
| 刊名 | journal of chemical physics
 |
| 出版日期 | 2015-05-07 |
| 卷号 | 142期号:17 |
| 英文摘要 | the o + o-2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (kies) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen kies important in the atmosphere. this work reports a quantum dynamics study of the title reactions on the newly constructed dawes-lolur-li-jiang-guo (dlljg) potential energy surface (pes). the thermal reaction rate coefficients of both the o-18 + o-32(2) and o-16 + o-36(2) reactions obtained using the dlljg pes exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified siebert-schinke-bittererova (mssb) pes. in addition, the calculated kie shows an improved agreement with the experiment. these results strongly support the absence of the "reef" structure in the entrance/exit channels of the dlljg pes, which is present in the mssb pes. the quantum dynamics results on both pess attribute the marked kie to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. the accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients. (c) 2015 aip publishing llc. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | physics, atomic, molecular & chemical |
| 研究领域[WOS] | physics |
| 关键词[WOS] | potential-energy surface ; rate constants ; dissociation threshold ; temperature-dependence ; schrodinger-equation ; rate coefficients ; cross-sections ; split operator ; wave-packet ; ozone |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000354258200028 |
| 公开日期 | 2016-05-09 |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/146219]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, Ctr Theoret & Computat Chem, Dalian 116023, Peoples R China 3.Univ Sci & Technol China, Ctr Adv Chem Phys, Hefei 230026, Peoples R China 4.Univ Sci & Technol China, Frontier Ctr Quantum Sci & Technol 2011, Hefei 230026, Peoples R China 5.Missouri Univ Sci & Technol, Dept Chem, Rolla, MO 65409 USA 6.Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA |
| 推荐引用方式 GB/T 7714 | Sun, Zhigang,Yu, Dequan,Xie, Wenbo,et al. Kinetic isotope effect of the O-16+O-36(2) and O-18+O-32(2) isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study[J]. journal of chemical physics,2015,142(17). |
| APA | Sun, Zhigang,Yu, Dequan,Xie, Wenbo,Hou, Jiayi,Dawes, Richard,&Guo, Hua.(2015).Kinetic isotope effect of the O-16+O-36(2) and O-18+O-32(2) isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study.journal of chemical physics,142(17). |
| MLA | Sun, Zhigang,et al."Kinetic isotope effect of the O-16+O-36(2) and O-18+O-32(2) isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study".journal of chemical physics 142.17(2015). |
入库方式： OAI收割
来源：大连化学物理研究所
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