A comparative theoretical study of heterocycle-functionalized tetrazolate- and tetrazolate-1-oxide-based dianionic salts

作者：Xiang Fang; Wu Qiong; Zhu Weihua^*; Xiao Heming

来源：Canadian Journal of Chemistry, 2013, 91(12): 1233-1242.

DOI：10.1139/cjc-2013-0287

• density functional theory
• crystal densities
• heats of formation
• detonation properties
• thermodynamics of salt formation

Density functional theory and volume-based thermodynamics calculations have been performed to study the crystal densities, heats of formation, energetic properties, thermodynamics of formation, and impact sensitivity for a series of heterocycle-functionalized tetrazolate-and tetrazolate1-oxide-based dianionic salts. The results show that the hydroxylammonium cation is better than the tetrazolium cation for increasing the densities and detonation performance of the tetrazolate dianionic salts. The salts containing series B (tetrazolate-1-oxide) have larger densities and detonation performance than corresponding ones containing series A (tetrazolate) with the same cation. Incorporating a zwitterionic N-oxide into the nitrogen system is helpful for increasing its density and detonation performance for each salt series, but it is not favorable for improving its heat of formation. The salt including the tetrazine-dioxide conjugated with two tetrazolide exhibits the best energetic performance. The salts containing the tetrazolium cation could be possibly synthesized by the proposed reactions. Some of the salts with the cation hydroxylammonium show lower impact sensitivity than RDX or HMX.

• 出版日期2013-12
• 单位南京大学