Synthesis, Characterization, Detonation Performance, and DFT Calculation of HMX/PNO Cocrystal Explosive

Abstract

A novel 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX)/pyridine-N-oxide (PNO) cocrystal at 1:1 molar ratio was synthesized by a solvent evaporation method, and its crystal structure was determined using X-ray diffraction (XRD). It crystallizes in the orthorhombic system with the Pbcn space group and cell parameters a = 12.712(3)Å, b = 9.315(3)Å, c = 12.909(3)Å. In addition, detonation performance of this cocrystal was estimated. The predicted detonation velocity and detonation pressure of this cocrystal are 7.47 km/s and 23.20 GPa, respectively, suggesting that it is less powerful than β-HMX. Finally, density functional theory, involving binding energy, atoms in molecule (AIM) theory, natural bond orbital (NBO) analysis, band structure, and density of states, was adopted to characterize the driving forces for the formation of this cocrystal. The results show that driving forces are dominated by the interactions between O atoms of PNO and methylene groups of HMX. It is expected that this research provides some bases for further HMX cocrystal design and preparation.