Xue-fei Lin, Cheng-ke Sun, Si-ya Yang, Zong-he Li. Theoretical Study of Decomposition Mechanism of Azoisobutyronitrile[J]. Chinese Journal of Chemical Physics , 2007, 20(3): 224-232. DOI: 10.1088/1674-0068/20/03/224-232
Citation:
Xue-fei Lin, Cheng-ke Sun, Si-ya Yang, Zong-he Li. Theoretical Study of Decomposition Mechanism of Azoisobutyronitrile[J]. Chinese Journal of Chemical Physics , 2007, 20(3): 224-232. DOI: 10.1088/1674-0068/20/03/224-232
Xue-fei Lin, Cheng-ke Sun, Si-ya Yang, Zong-he Li. Theoretical Study of Decomposition Mechanism of Azoisobutyronitrile[J]. Chinese Journal of Chemical Physics , 2007, 20(3): 224-232. DOI: 10.1088/1674-0068/20/03/224-232
Citation:
Xue-fei Lin, Cheng-ke Sun, Si-ya Yang, Zong-he Li. Theoretical Study of Decomposition Mechanism of Azoisobutyronitrile[J]. Chinese Journal of Chemical Physics , 2007, 20(3): 224-232. DOI: 10.1088/1674-0068/20/03/224-232
Department of Chemistry, Qujing Normal University, Qujing 655000, China
2.
Department of Chemistry, Beijing Normal University, Beijing 100875, China
Funds: This work was supported by the National Natural Science Foundation of China (No.29773007), the Science Foundation of Teaching and Scientific Research Pilot of Yunnan Province (No.200401,) and the Natural Science Foundation of Yunnan Province, China(No.2006C0083M)
The decomposition mechanisms of azoisobutyronitrile were systematically investigated. Density function theory B3LYP/6-311G*, B3LYP/6-311+G* and BHandH/6-31+G** methods were employed to optimize the geometry parameters of the reactants, transition states, possible intermediates and products based on the detailed potential energy surfaces scanned with AM1. The reaction mechanisms were also analyzed theoretically. The results indicate that the decomposition of azoisobutyronitrile is a two-bond (three body) synchronouscleavage process in the ground state (CH3)2CNC-N=N-CCN(CH3)2→2(CH3)2CNC·+N2; and is a twobond asynchronous cleavage process while in the triple state (CH3)2CNCN=N-CCN(CH3)2→(CH3)2CN{CN=N· · ·CCN(CH3)2→2(CH3)2CNC·+N2. The calculations rationalize and verify all experimental facts.
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