Theoretical Studies on the Heats of Formation, Detonation Properties, and Pyrolysis Mechanisms of Energetic Cyclic Nitramines

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• 作者：Fang Wang ; Guixiang Wang ; Hongchen Du ; Jianying Zhang ; Xuedong Gong
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：December 1, 2011
• 年：2011
• 卷：115
• 期：47
• 页码：13858-13864
• 全文大小：841K
• 年卷期：v.115,no.47(December 1, 2011)
• ISSN：1520-5215

文摘

Density functional theory calculations were performed to find comprehensive relationships between the structures and performance of a series of highly energetic cyclic nitramines. The isodesmic reaction method was employed to estimate the heat of formation. The detonation properties were evaluated by using the Kamlet鈥揓acobs equations based on the theoretical densities and HOFs. Results indicate the N鈥揘O₂ group and aza N atom are effective substituents for enhancing the detonation performance. All cyclic nitramines except C11 and C21 exhibit better detonation performance than HMX. The decomposition mechanism and thermal stability of these cyclic nitramines were analyzed via the bond dissociation energies. For most of these nitramines, the homolysis of N鈥揘O₂ is the initial step in the thermolysis, and the species with the bridged N鈥揘 bond are more sensitive than others. Considering the detonation performance and thermal stability, twelve derivatives may be the promising candidates of high energy density materials (HEDMs). The results of this study may provide basic information for the further study of this kind of compounds and molecular design of novel HEDMs.