Discriminative Mechanical and Thermal Response of the H–N Bonds for the Energetic LLM-105 Molecular Assembly

Molecular interactions in energetic materials form the key not only to the “structure stability, energy storage, ignition, and detonation” dynamics but also to the sensitivity to the loading of perturbation and the power intensity of radiation for the energetic substance, with the nature of the interactions remaining elusive. With the aid of perturbative Raman spectroscopy and the pressure-resolved density functional theory, we uncovered that the H–N bond of the intermolecular O:H–N bonds for LLM-105 shares the same negative compressibility and thermal expansivity of the H–O bond for the coupling O:H–O bond of water [Phys. Rep. 2023, 998, 1–68]. In contrast, the dangling H–N bond vibrating at a 3440 cm–1 high frequency does otherwise due to the absence of coupling interaction and the undercoordination-driven bond contraction. These findings should deepen our insight into interactions involving electron lone pairs and offer an efficient means for discriminating the performance of individual bonds.