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以4种新型三呋咱并氧(氮)杂环庚三烯分子为研究对象,采用密度泛函理论B3LYP/6-31G(d,p)方法优化了其结构,得到了最优几何构型,并在振动分析的基础上求得体系的振动频率和IR谱,通过键级和键离解能(BDE)计算考察了4种分子的稳定性,在密度和生成焓计算基础上利用Kamlet-Jacobs公式预估了其性能。结果表明:当呋咱环上的N原子被氧化形成N→O配位键,与该N原子相连的O—N键和C—N键键长增大,与该N原子相间的N—O键和C—C键键长减小,除了氧化呋咱环上N—O—N键角显著减小外,其余键角无明显变化,二面角的变化幅度非常小,整个分子近乎在同一平面上;4个化合物的热稳定性均较好,但当呋咱环被氧化成为氧化呋咱环后,化合物的热稳定性显著降低,其热稳定性顺序为TFZN-1>TFZO-1>>TFZN-2≈TFZO-2;呋咱环被氧化后能够大幅度提高炸药的爆轰性能,预估爆速在7600~8100 m/s范围,且与实测值吻合较好。
In this paper, four kinds of novel 3-furazanoxoheptaheptahenes were studied. Their structures were optimized by density functional theory B3LYP / 6-31G (d, p) The vibration frequency and IR spectrum of the system were calculated based on the vibration analysis. The stability of the four kinds of molecules was investigated by the bond-level and bond-dissociation energy (BDE) calculations. Based on the density and enthalpy of formation, Kamlet-Jacobs The formula predicts its performance. The results show that when the N atoms on the furazan ring are oxidized to form N → O coordination bonds, the bond lengths of the O-N and C-N bonds with the N atom increase and the N-O Bond and C-C bonds decreased, except for the N-O-N bond angle on the oxfurazan ring was significantly reduced, the remaining bond angle did not change significantly, the dihedral angle of the change is very small, the entire molecule is almost the same On the plane, the thermal stability of the four compounds are good, but when the furazan ring is oxidized to furazan oxide ring, the thermal stability of the compounds is significantly reduced. The thermal stability of the compounds is TFZN-1> TFZO-1> > TFZN-2≈TFZO-2. The oxidation rate of furazan ring can greatly improve the detonation performance of explosives. The predicted detonation velocity is in the range of 7600 ~ 8100 m / s, which is in good agreement with the measured data.