Cao Wenli, Ding Zimei, Hang Xiaojing, Xu Kangzhen, Song Jirong, Huang Jie, Guo Jiajia
School of Chemical Engineering, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University Xi'an 710069 China
Conservation Technology Department, The Palace Museum Beijing 100009 China.
RSC Adv. 2018 Jun 29;8(42):23805-23816. doi: 10.1039/c7ra13424j. eCollection 2018 Jun 27.
Density function theory has been employed to systemically study 4,4'-azo-1-1,2,4-triazol-5-one (ZTO) and its six nitrogen-rich salts at two different calculated levels (B3LYP/6-31G(d,p) and B3PW91/6-31G(d,p)). Their optimized geometries, electronic structures and molecular electrostatic potentials were further studied. Based on the two computed methods, the results of the optimized geometries show that the calculated structure of each compound adopted at the two different levels are rather similar except salt 7 with some differences. The values of the energy gaps indicate that compound 3 has the highest reactivity among salts 2-7. The crystal densities were corrected using the Politzer approach based on these two optimized levels. The density values with slight deviation indicate that the two calculated levels are applicable and the results are convincible. Based on the isodesmic reactions and Born-Haber energy cycle, the solid-phase heats of formation (HOFs) were predicted. Detonation parameters were evaluated using the Kamlet-Jacobs equations on the foundations of the calculated densities and HOFs. The results manifest that salt 2 exhibits the best detonation performance due to its highest density (1.819 g cm), followed by salt 6. Moreover, impact sensitivities of compounds 1-7 were assessed using the calculated values to correlate with . Combining the detonation performance with safety, 1-7 exhibit good comprehensive properties and might be screened as a composition of modern nitrogen-rich energetic compounds.
采用密度泛函理论在两种不同计算水平（B3LYP/6-31G(d,p) 和 B3PW91/6-31G(d,p)）下系统研究了 4,4'-偶氮-1,2,4-三唑-5-酮（ZTO）及其六种富氮盐。进一步研究了它们的优化几何结构、电子结构和分子静电势。基于这两种计算方法，优化几何结构的结果表明，除盐 7 存在一些差异外，两种不同水平下各化合物的计算结构相当相似。能隙值表明化合物 3 在盐 2 - 7 中具有最高的反应活性。基于这两个优化水平，使用波利策尔方法校正了晶体密度。略有偏差的密度值表明这两种计算水平是适用的，结果是可信的。基于等键反应和玻恩-哈伯能量循环，预测了固相生成热（HOFs）。基于计算得到的密度和 HOFs，使用卡姆雷特-雅各布斯方程评估爆轰参数。结果表明，盐 2 因其最高密度（1.819 g/cm³）表现出最佳的爆轰性能，其次是盐 6。此外，使用计算值评估了化合物 1 - 7 的撞击感度，并与……相关联。综合爆轰性能和安全性，1 - 7 表现出良好的综合性能，可能被筛选为现代富氮高能化合物的组成成分。
