Department of Chemistry, Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China.
J Phys Chem A. 2011 Dec 1;115(47):13858-64. doi: 10.1021/jp2047536. Epub 2011 Nov 7.
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-Jacobs equations based on the theoretical densities and HOFs. Results indicate the N-NO(2) 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-NO(2) is the initial step in the thermolysis, and the species with the bridged N-N 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.
采用密度泛函理论计算方法，研究了一系列高能环状硝胺的结构与性能之间的综合关系。采用均裂反应法估算生成热。基于理论密度和 HOFs，利用 Kamlet-Jacobs 方程评估了爆轰性能。结果表明，N-NO2 基团和氮杂原子是增强爆轰性能的有效取代基。除 C11 和 C21 外，所有环状硝胺的爆轰性能均优于 HMX。通过键离解能分析了这些环状硝胺的分解机理和热稳定性。对于大多数硝胺，N-NO2 的均裂是热解的初始步骤，具有桥接 N-N 键的物质比其他物质更敏感。考虑到爆轰性能和热稳定性，有 12 种衍生物可能是高能密度材料（HEDM）的有前途的候选材料。本研究结果可为进一步研究此类化合物和新型 HEDM 的分子设计提供基础信息。
