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采用Gaussian 98中的DFT-B3LYP方法在6-31G(d,p)基组水平下对3,4-双(3′-硝基苯-1′-基)氧化呋咱进行结构全优化及Wiberg键级计算,并采用TG-DSC-FITR-MS分析方法对其热分解机理进行研究。在优化的几何构型中,氧化呋咱环的六个原子为共平面结构,其中O—N配位键与双键相似。呋咱环内靠近配位氧的O—N键级最弱,为0.8769。结合热解气相产物分析与键级计算推测3,4-双(3′-硝基苯-1′-基)氧化呋咱的热解初始步骤为氧化呋咱环内N—O键的断裂;推测其热分解反应历程为氧化呋咱环首先开环分解为气体小分子及硝基苯,硝基苯再经自由基分解或异构化为亚硝基氧苯分解。
The structural optimization of 3,4-bis (3’-nitrophenyl-1’-yl) furazan was carried out using the DFT-B3LYP method in Gaussian 98 at the 6-31G (d, p) Key-level calculation, and TG-DSC-FITR-MS analysis of its thermal decomposition mechanism. In the optimized geometry, the six atoms of the furazan ring are coplanar structures, with the O-N coordination bonds being similar to the double bonds. The O-N bond in the furazan ring near the coordination oxygen is the weakest, 0.8769. According to the pyrolysis gas phase product analysis and key-level calculation, it is speculated that the initial pyrolysis of 3,4-bis (3’-nitrophenyl-1’-yl) furan oxide is the cleavage of the N-O bond in the furazan ring. It is speculated that the thermal decomposition reaction process is the first ring-opening decomposition of furazan ring into small molecules of gas and nitrobenzene. The nitrobenzene is decomposed by radical or isomerization to nitrosoxyphenyl.