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Citation: Li Lai-Cai, Qian Yi-Ming, Zhu Yuan-Qiang, Tian An-Min. Theoretical Study on the Reaction Mechanism of the CH3 Radical with HNCO[J]. Acta Physico-Chimica Sinica, ;2004, 20(03): 228-232. doi: 10.3866/PKU.WHXB20040302 shu

Theoretical Study on the Reaction Mechanism of the CH3 Radical with HNCO

1.
Department of Chemistry, Sichuan Normal University, Chengdu　610066;Department of Chemistry, Sichuan University, Chengdu　610064

Received Date: 10 July 2003
Available Online: 15 March 2004

Ab initio UMP2 method was used to study the reaction mechanism of CH3 radical with HNCO. The geometric configurations of reactants, products, intermediates and transition states were optimized at UMP2(full)/6-311＋＋G** level. The results show that the reaction of CH3 radical with HNCO has three pathways: (1) CH3 radical reacts with HNCO to form a hydrogen-bond complex M of which the relative stable energy is 4.56 kJ•mol－1,and then forms another complex M′through a transition state TS, and breaks down into CH4 and NCO radical in the end. (2) CH3 radical reacts with HNCO to form a stable trans- intermediate (trans-int), then through a transition state (trans-ts) breaks down into CH3NH and CO. (3) CH3 radical reacts with HNCO to form a stable cis-intermediate (cis-int), and then through a transition state(cis-ts) breaks down into CH3NH and CO. Comparing the activation energy of the three pathways, we can draw a conclusion that the pathway of forming CH4 and NCO radical is more feasible.
- HNCO;Radical reaction;Ab initio UMP2 method;Hydrogen-bond complex
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