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题名: Competitive reaction pathways of C2Cl3 + NO via four-membered ring and bicyclic ring intermediates
作者: Liu, Kunhui1;  Song, Di1;  Zhao, Shaolei1;  Wang, Sufan2;  Yang, Chunfan1;  Su, Hongmei1
刊名: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
发表日期: 2011
DOI: 10.1039/c0cp01192d
卷: 13, 期:6, 页:1990-2000
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: The products and mechanisms of the atmospherically and environmentally important reaction, C2Cl3 + NO, are investigated comprehensively by step-scan time-resolved Fourier transform infrared emission spectroscopy and the CCSD(T)/6-311 + G(d)//B3LYP/6-311G(d) level of electronic structure calculations. Vibrationally excited products of Cl2CO, ClNCO, CCl3NCO and NCO have been observed in the IR emission spectra. Cyclic intermediates are found to play important roles leading to the rich variety of the chemical transformations of the reaction. Mainly two competitive reaction pathways are revealed: the four-membered ring intermediate pathway leading to the products Cl2CO + ClCN which is essentially barrierless and the bicyclic ring intermediate pathway leading to the product channels of ClNCO + CCl2, CCl3NCO and CCl3 + NCO which is rate-limited by a barrier of 42.9 kJ mol(-1) higher than the reactants. By photolyzing the precursor at 248 and 193 nm, respectively, C2Cl3 radicals with different internal energy are produced to observe the product branching ratios as a function of reactant energy. The Cl2CO channel via the four-membered ring intermediate pathway is shown to be overwhelmingly dominant at low energy (temperature) but become less important at high energy while the ClNCO and CCl3NCO channels via the bicyclic ring intermediate pathway are greatly enhanced and compete effectively. The experimental observation of the products and their branching ratios varying with reactant energy is well consistent with the calculated potential energy profiles.
关键词[WOS]: NITRIC-OXIDE ;  NM PHOTODISSOCIATION ;  MOLECULAR-OXYGEN ;  INFRARED-SPECTRA ;  VINYL RADICALS ;  KINETICS ;  NO ;  CL ;  SPECTROSCOPY ;  ACETYLENE
语种: 英语
WOS记录号: WOS:000286628200007
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142688
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, Beijing Natl Lab Mol Sci, Inst Chem, Beijing 100190, Peoples R China
2.Anhui Normal Univ, Coll Chem & Mat Sci, Wuhu 241000, Peoples R China

Recommended Citation:
Liu, Kunhui,Song, Di,Zhao, Shaolei,et al. Competitive reaction pathways of C2Cl3 + NO via four-membered ring and bicyclic ring intermediates[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2011,13(6):1990-2000.
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