典型插入反应体系的微观动力学理论研究
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- 英文论文题名：Theoretical Study on the Dynamics of Prototypical Insertion Reactions
- 论文作者：曹剑炜 ; 申志涛 ; 吴亚楠 ; 边文生
- 英文论文作者：Jianwei Cao ; Zhitao Shen ; Yanan Wu ; Wensheng Bian ; Institute of Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院化学研究所;
- 论文关键词：插入反应 ; 量子反应动力学 ; 准经典轨线 ; 反应机理
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十四分会：化学动力学
- 语种：中文
- 分类号：O643.1
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十四分会 ; 化学动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：186k
- 原文格式：D
- 会议级别：全国
摘要
插入反应在有机化学,燃烧化学中扮演着重要角色,一直为实验和理论工作者所关注。本文中我们以C(~1D)+H_2→CH+H及其同位素反应为典型来研究插入反应。本课题组成功构建了C(~1D)H_2体系单重电子基态(?~1A′)[1]和第一单重电子激发态(b~1A″)的新的高精度全局从头算势能面。该势能面的特色在于对范德华相互作用以及锥形交叉区域的准确描述。基于这两个势能面,我们对该体系进行了详细的量子反应动力学和准经典轨线计算,得到了积分截面、微分截面、产物态分布和热反应速率等动力学信息。[2]我们的研究澄清了目前理论计算和实验结果之间的差异,揭示了该体系中有趣的微观动力学现象,并在量子态层次发现了新的反应机理,将有助于深化人们对插入反应的认识。
The insertion reactions play a significant role in organic and combustion chemistry, and have been the subject of many experimental and theoretical studies. In this work, we take the C(~1D)+H_2 reaction and its isotopic variants as prototypes to study the insertion reactions. Recently the new global ab initio potential energy surfaces(PESs) for the ?~1A′ [1] and b~1A″ states of the C(~1D)H_2 reactive system have been constructed by our group, the main advantage of which is the very good description of the regions of van der Waals interactions and around conical intersections. Based upon these PESs, we perform detailed quantum dynamics and quasiclassical trajectory calculations. Various dynamical and kinetic quantities such as integral cross sections, differential cross sections, product rovibrational state distributions and rate coefficients are investigated. Interesting dynamical phenomena are revealed, new reaction mechanisms at the quantum state level are analyzed, and the differences between the previous theoretical results and experimental measurements are clarified. Our calculations will deepen the understanding of insertion reactions.
The insertion reactions play a significant role in organic and combustion chemistry, and have been the subject of many experimental and theoretical studies. In this work, we take the C(~1D)+H_2 reaction and its isotopic variants as prototypes to study the insertion reactions. Recently the new global ab initio potential energy surfaces(PESs) for the ?~1A′ [1] and b~1A″ states of the C(~1D)H_2 reactive system have been constructed by our group, the main advantage of which is the very good description of the regions of van der Waals interactions and around conical intersections. Based upon these PESs, we perform detailed quantum dynamics and quasiclassical trajectory calculations. Various dynamical and kinetic quantities such as integral cross sections, differential cross sections, product rovibrational state distributions and rate coefficients are investigated. Interesting dynamical phenomena are revealed, new reaction mechanisms at the quantum state level are analyzed, and the differences between the previous theoretical results and experimental measurements are clarified. Our calculations will deepen the understanding of insertion reactions.
引文
[1]Zhang,C.;Fu,M.;Shen,Z.;Ma,H.;Bian,W.J.Chem.Phys.2014,140:234301.
[2]Wu,Y.;Zhang,C.;Cao,J.;Bian,W.J.Phys.Chem.A 2014,118:4235.
[2]Wu,Y.;Zhang,C.;Cao,J.;Bian,W.J.Phys.Chem.A 2014,118:4235.