This review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our own first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.

Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1), and 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO₂ homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.

The title compound 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) was synthesized by: (1) by reaction of 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1) with gaseous ammonia in toluene and (2) by partial oxidation of 3,4-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BAFF-1) with 35% H₂O₂ in concentrated H₂SO₄.

Optical absorption measurements are combined with electronic structure calculations to explore photochemistry of an α-Al₂O₃-PETN interface formed by a nitroester (pentaerythritol tetranitrate, PETN, C₅H₈N₄O₁₂) and a wide band gap aluminum oxide (α-Al₂O₃) substrate. The first principles modeling is used to deconstruct and interpret the α-Al₂O₃-PETN absorption spectrum that has distinct peaks attributed to surface F⁰-centers and surface—PETN transitions. We predict the low energy α-Al₂O₃ F⁰-center—PETN transition, producing the excited triplet state, and α-Al₂O₃ F⁰-center—PETN charge transfer, generating the PETN anion radical. This implies that irradiation by commonly used lasers can easily initiate photodecomposition of both excited and charged PETN at the interface. The feasible mechanism of the photodecomposition is proposed.

Everybody knows TNT, the most widely used explosive material and a universal measure of the destructiveness of explosions. A long history of use and extensive manufacture of toxic TNT leads to the accumulation of these materials in soil and groundwater, which is a significant concern for environmental safety and sustainability. Reliable and cost-efficient technologies for removing or detoxifying TNT from the environment are lacking. Despite the extreme urgency, this remains an outstanding challenge that often goes unnoticed. We report here that highly controlled energy release from explosive molecules can be accomplished rather easily by preparing TNT–perovskite mixtures with a tailored perovskite surface morphology at ambient conditions. These results offer new insight into understanding the sensitivity of high explosives to detonation initiation and enable many novel applications, such as new concepts in harvesting and converting chemical energy, the design of new, improved energetics with tunable characteristics, the development of powerful fuels and miniaturized detonators, and new ways for eliminating toxins from land and water.