Structure, Physicochemical Properties, and Density Functional Theory Calculation of High-Energy-Density Materials Constructed with Intermolecular Interaction: Nitro Group Charge Determines Sensitivity

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• 作者：Xiangyu Liu ; Zhiyong Su ; Wenxin Ji ; Sanping Chen ; Qing Wei ; Gang Xie ; Xuwu Yang ; Shengli Gao
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：October 16, 2014
• 年：2014
• 卷：118
• 期：41
• 页码：23487-23498
• 全文大小：657K
• ISSN：1932-7455

文摘

Four nitro-containing energetic compounds, cocrystal of AT路DNBA (1), salt of MA路DNSA (2), salt of AG路DNBA路H₂O (3), and salt of DAT路DNSA H₂O (4), are synthesized and structurally characterized based on supramolecular interactions (AT, 4-amino-1,2,4-triazole; DNBA, 3,5-dinitrobenzoic acid; MA, melamine; DNSA, 3,5-dinitrosalicylic acid; AG, amino guanidine; DAT, 3,5-diamino-1,2,4-triazole). The physicochemical properties of the compounds are theoretically and experimentally investigated in detail. The optimized structures, molecular total energies, frontier orbit energies, and charge densities of 1鈥?b>4 are calculated by theoretical methods. The experimental results indicate that all compounds exhibit good thermostability and low sensitivity. It is worth noting that the values of impact sensitivity are measured to be 30, >40, 38, and >40 J for 1, 2, 3, and 4, respectively, which correspond well to the order of nitro group charge (Q_Nitro) calculated by density functional theory. The detonation performances of 1鈥?b>4 are discussed; in particular, 1 and 2 exhibit heats of detonation (2.191 kcal鈥塯^鈥? for 1 and 2.214 kcal鈥塯^鈥? for 2) superior to those of classical nitro-rich compounds. In addition, the nonisothermal thermokinetic parameters are obtained by Kissinger and Ozawa methods, and the standard molar enthalpies of formation are calculated from the determination of constant volume combustion energies.