Theoretical Study on the Structure and Properties of Composite Energetic Groups

doi:10.6023/A26040105

Abstract

Breaking the development bottlenecks of traditional energetic materials has become an urgent problem to be solved in recent years. In general, energetic materials are composed of energetic groups and molecular skeletons. At present, most design strategies for energetic molecules focus on the construction of novel molecular skeletons. Inspired by the unconventional complex energetic groups reported in the literature, this study focused on the design of new “composite energetic groups”. A total of 72 initial structures were obtained by combining traditional energetic groups. Theoretical calculations on their molecular structures, initial thermal decomposition mechanisms were performed via density functional theory (DFT) using the Gaussian16 program. Excellent kinetic stability ensures a sufficiently high thermal decomposition temperature and favorable chemical stability, which are essential prerequisites for the practical application of energetic molecules. Identifying accurate trigger bonds and reliable decomposition mechanisms is critical for determining the initial decomposition energy barriers. Multiple potentially fractured chemical bonds and various cleavage pathways were considered, including homolysis, heterolysis, group migration, and elimination. The Kamlet-Jacobs (KJ) equation and the EXPLO5 program were adopted to calculate detonation velocity and detonation pressure. Subsequently, 39 energetic groups were screened out based on energetic performance and kinetic stability, all possessing an initial decomposition energy barrier of ≥30 kcal/mol, among which 34 were unprecedented new groups. For five experimentally synthesized structures, detailed comparisons demonstrated that the calculated thermal stability results were in excellent agreement with experimental data. Furthermore, molecular design was carried out using alkane skeletons and polyamine skeletons. It is revealed that the intramolecular strain and steric hindrance dominated by alkane skeletons, as well as the hyperconjugation effect, exert a significant influence on the kinetic stability of the final energetic molecules. All these molecules exhibit a density >2.0 g/cm³, a detonation velocity >8000 m/s, and a detonation pressure >33 GPa.

Key words: composite energetic groups, energetic materials, molecular design, theoretical study, kinetic stability

Cite this article

Ma Lingling, Ling Lin, Li Yuxue, Lu Long. Theoretical Study on the Structure and Properties of Composite Energetic Groups[J]. Acta Chimica Sinica, doi: 10.6023/A26040105.

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