三呋咱并氧(氮)杂环庚三烯的密度泛函理论研究  

A DFT study of bifurazano [b, f] furoxano [d] oxa(azo) cyclohetpatriene

作　　者：廉鹏[1] 来蔚鹏[1] 吕剑[1] 刘英哲[1] 尉涛[1] 王伯周[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《计算机与应用化学》2016年第8期909-914,共6页Computers and Applied Chemistry

基　　金：国防基础科研计划资助项目(B0920110005)

摘　　要：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。Four novel bifurazano [b, f] furoxano [d] oxa （azo） cyclohetpatriene compounds （TFZO-1, TFZO-2, TFZN-1, and TFZN-2） were theoretically studied as potential high energetic density materials. The stable geometries of the four compounds were optimized at B3LYP/6-31G （d, p） theoretical level. Their IR spectra were obtained on the basis of vibrational analysis calculations. The bond dissoci- ation energies （BDEs） of the thermolysis trigger bonds were computed to evaluate their thermal stabilities. The densities, solid-phase enthalpies of formation and detonation properties were predicted. The results show that the N atom in furoxan cycle will affect the bond lengths of the O^N, C--N, and C--C bonds in the same furoxan cycle when it was oxidized to form the N---~O coordination bond. The changes of dihedral angles and bond angles exception the N---O--N in furoxan almost can be neglect, and the whole molecules are closed to be coplanar. Large BDEs indicate the high thermal stabilities of these compounds, and the thermal stabilities will evidently decrease when the furazan cycle was oxidized. The order is TFZN-I〉TFZO-I〉〉TFZN-2≈TFZO-2. The oxidation of furazan cycle will improve the detonation properties, and match the experimental value on the whole.

关 键 词：三呋咱并氧(氮)杂环庚三烯 结构 性能 热稳定性 

分 类 号：TQ015.9[化学工程] TP391.9[自动化与计算机技术—计算机应用技术]