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题名: Quasiclassical trajectory study of H+SiH4 reactions in full-dimensionality reveals atomic-level mechanisms
作者: Cao, Jianwei1, 2;  Zhang, Zhijun1, 2;  Zhang, Chunfang1, 2;  Liu, Kun1;  Wang, Manhui1;  Bian, Wensheng1
关键词: potential energy surface ;  reaction dynamics
刊名: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
发表日期: 2009-08-11
DOI: 10.1073/pnas.0903934106
卷: 106, 期:32, 页:13180-13185
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology
类目[WOS]: Multidisciplinary Sciences
研究领域[WOS]: Science & Technology - Other Topics
英文摘要: This work elucidates new atomic-level mechanisms that may be common in a range of chemical reactions, and our findings are important for the understanding of the nature of polyatomic abstraction and exchange reactions. A global 12-dimensional ab initio potential energy surface (PES), which describes both H+SiH4 abstraction and exchange reactions is constructed, based on the modified Shepard interpolation method and UCCSD(T)/cc-pVQZ energy calculations at 4,015 geometries. This PES has a classical barrier height of 5.35 kcal/mol for abstraction (our best estimate is 5.35 +/- 0.15 kcal/mol from extensive ab initio calculations), and an exothermicity of -13.12 kcal/mol, in excellent agreement with experiment. Quasiclassical trajectory calculations on this new PES reveal interesting features of detailed dynamical quantities and underlying new mechanisms. Our calculated product angular distributions for exchange are in the forward hemisphere with a tail sideways, and are attributed to the combination of three mechanisms: inversion, torsion-tilt, and side-inversion. With increase of collision energy our calculated angular distributions for abstraction first peak at backward scattering and then shift toward smaller scattering angles, which is explained by a competition between rebound and stripping mechanisms; here stripping is seen at much lower energies, but is conceptually similar to what was observed in the reaction of H+CD4 by Zare and coworkers [Camden JP, et al. (2005) J Am Chem Soc 127: 11898-11899]. Each of these atomic-level mechanisms is confirmed by direct examination of trajectories, and two of them (torsion-tilt and side-inversion) are proposed and designated in this work.
关键词[WOS]: POTENTIAL-ENERGY SURFACES ;  REACTION DYNAMICS ;  RATE CONSTANTS ;  ANGULAR-DISTRIBUTIONS ;  EXCHANGE-REACTIONS ;  SIMPLEST REACTION ;  HYDROGEN-ATOMS ;  CARBON-ATOM ;  ABSTRACTION ;  SIH4
语种: 英语
WOS记录号: WOS:000268877300009
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/141248
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
2.Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China

Recommended Citation:
Cao, Jianwei,Zhang, Zhijun,Zhang, Chunfang,et al. Quasiclassical trajectory study of H+SiH4 reactions in full-dimensionality reveals atomic-level mechanisms[J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,2009,106(32):13180-13185.
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