ICCAS OpenIR
Competitive reaction pathways of C2Cl3 + NO via four-membered ring and bicyclic ring intermediates
Liu, Kunhui1; Song, Di1; Zhao, Shaolei1; Wang, Sufan2; Yang, Chunfan1; Su, Hongmei1
2011
Source PublicationPHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN1463-9076
Volume13Issue:6Pages:1990-2000
AbstractThe 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.
DOI10.1039/c0cp01192d
Indexed BySCI
Language英语
WOS IDWOS:000286628200007
PublisherROYAL SOC CHEMISTRY
Citation statistics
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/73632
Collection中国科学院化学研究所
Corresponding AuthorSu, Hongmei
Affiliation1.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
GB/T 7714
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.
APA Liu, Kunhui,Song, Di,Zhao, Shaolei,Wang, Sufan,Yang, Chunfan,&Su, Hongmei.(2011).Competitive reaction pathways of C2Cl3 + NO via four-membered ring and bicyclic ring intermediates.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,13(6),1990-2000.
MLA Liu, Kunhui,et al."Competitive reaction pathways of C2Cl3 + NO via four-membered ring and bicyclic ring intermediates".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 13.6(2011):1990-2000.
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