Trapped Abstraction in the O(1D) + CHD3 → OH + CD3 Reaction

被引：25

作者：

Yang, Jiayue ^{[1
]}

Shao, Kejie ^{[1
]}

Zhang, Dong ^{[1
]}

Shuai, Quan ^{[1
]}

Fu, Bina ^{[1
]}

Zhang, Dong H. ^{[1
]}

Yang, Xueming ^{[1
]}

机构：

[1] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2014年 / 5卷 / 18期

基金：

中国国家自然科学基金;

关键词：

CROSSED MOLECULAR-BEAM; AB-INITIO; INSERTION REACTION; REACTION DYNAMICS; COLLISION ENERGY; CHLORINE ATOM; MECHANISM; SCATTERING; PLUS; RESONANCES;

D O I：

10.1021/jz5016923

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Despite significant progress made in past decades, it is still challenging to elucidate dynamics mechanisms for polyatomic reactions, in particular, involving complex formation. The reaction of O(D-1) with methane has long been regarded as a prototypical polyatomic system of direct insertion reaction in which the O(D-1) atom can insert into the C-H bond of methane to form a "hot" methanol intermediate before decomposition. Here, we report a combined theoretical and experimental study on the O(D-1) + CHD3 reaction, on which good agreement between theory and experiment is achieved. Our study revealed that this complex-forming reaction actually proceeds via a trapped abstraction mechanism, rather than an insertion mechanism as has long been thought. We anticipate that this reaction mechanism should also be responsible for the reaction of O(D-1) with ethane and propane, as well as many other chemical reactions with deep wells in the interaction region.

引用

页码：3106 / 3111

页数：6

共 48 条

[1] Dynamics of the simplest chlorine atom reaction: An experimental and theoretical study [J].