Theoretic design of 1,2,3,4-tetrazine-1,3-dioxide-based high-energy density compounds with oxygen balance close to zero
Theoretic design of 1,2,3,4-tetrazine-1,3-dioxide-based high-energy density compounds with oxygen balance close to zero
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DOI：
10.1007/s11224-012-0190-0
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发表时间：
2013-01
影响因子：
1.7
通讯作者：
Qiong Wu;Yongfei Pan;Xuelan Xia;Yuling Shao;Weihua Zhu;Heming Xiao
中科院分区：
文献类型：
--
作者：
Qiong Wu;Yongfei Pan;Xuelan Xia;Yuling Shao;Weihua Zhu;Heming Xiao
采用密度泛函理论方法研究了一系列具有不同取代基和桥基的1,2,3,4-四嗪-1,3-二氧化物衍生物的生成热、电子结构、能量性质和热稳定性。发现- NO2、- c (NO2)3和- N=N -基团对衍生物的hof的提高起着非常重要的作用。取代基对最高已占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）能级和HOMO - LUMO间隙的影响与不同取代基和桥的影响是耦合的。计算的爆轰速度和压力表明，- NO2、- nf2、- ono2、- c (NO2)3或- nh3基团是提高衍生物爆轰性能的有效结构单元。对几个相对弱键的键解离能分析表明，在母环中加入- NO2、- nf2、- ono2、- c (NO2)3和- N=N -基团降低了它们的热稳定性。考虑到爆轰性能和热稳定性，18种化合物可以被认为是最有可能被合成和作为高能密度化合物使用的目标化合物。其中，有四种化合物的氧平衡为零。这些结果为新型高能化合物的分子设计提供了基础信息。
Density functional theory method was used to study the heats of formation (HOFs), electronic structure, energetic properties, and thermal stability for a series of 1,2,3,4-tetrazine-1,3-dioxide derivatives with different substituents and bridge groups. It is found that the groups –NO2, –C(NO2)3, and –N=N– play a very important role in increasing the HOFs of the derivatives. The effects of the substituents on the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels and HOMO–LUMO gaps are coupled to those of different substituents and bridges. The calculated detonation velocities and pressures indicate that the group –NO2, –NF2, –ONO2, –C(NO2)3, or –NH– is an effective structural unit for enhancing the detonation performance for the derivatives. An analysis of the bond dissociation energies for several relatively weak bonds indicates that incorporating the groups –NO2, –NF2, –ONO2, –C(NO2)3, and –N=N– into parent ring decreases their thermal stability. Considering the detonation performance and thermal stability, 18 compounds may be considered as the target compounds holding the greatest potential for synthesis and use as high-energy density compounds. Among them, the oxygen balances of four compounds are equal to zero. These results provide basic information for the molecular design of the novel high-energy compounds.