Thermal and shock-induced decomposition mechanisms of stereoisomeric energetic compounds: A ReaxFF-lg molecular dynamics study of mannitol hexanitrate (MHN) and sorbitol hexanitrate (SHN)

SF Zhu and SF Zheng and EL Liu and CW Yang and SH Zhang and RJ Gou, MATERIALS CHEMISTRY AND PHYSICS, 344, 131133 (2025).

DOI: 10.1016/j.matchemphys.2025.131133

Thermal and shock response mechanisms of mannitol hexanitrate (MHN) and sorbitol hexanitrate (SHN), a group of stereoisomeric nitric ester compounds, were investigated to enhance the understanding of the structural-property relationship of energetic materials. The decomposition mechanism of MHN and SHN under four temperature conditions (300-3000 K, 2000 K, 2500 K, and 3000 K) and three shock velocities (7 km/s, 8 km/s, and 9 km/s) are investigated through ReaxFF-lg molecular dynamics simulations, and the potential energy, decomposition reactions, products, and clusters were analyzed. Results revealed that MHN exhibits slower decomposition rates and superior thermal stability compared to SHN, with significant differences in potential energy peaks and reaction pathways. Under shock loading, SHN underwent faster decomposition, indicating distinct physical and chemical processes. Bond dissociation energy and Hirshfeld surface analyses highlighted that MHN's higher O-NO2 bond dissociation energy and stronger intermolecular interactions contribute to its slower decomposition. These findings provide valuable insights into the decomposition mechanisms of stereo-isomeric energetic materials, facilitating the rational design of explosives with improved safety and performance.

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