Theoretical Study of Nitrogen‑Rich Energetic Salts With Triply Fused Rings as Anions

ABSTRACT Ten tricyclic fused‐ring anionic structures were designed and combined with fused‑ring cations or two inorganic cations to form energetic salts. Geometrical structures of all ions were optimized by the DFT‐B3LYP method. The heats of formation were determined through isodesmic reactions, and the densities of the salts were calculated. The detonation performance was evaluated using the Kamlet–Jacobs formula. The deprotonation energies of these 10 anions were also calculated to assess their synthetic feasibility. It was found that using ammonium and protonated hydroxylammonium as cations increases the density of the energetic salts, resulting in overall better detonation performance for these salts compared to those with organic cations. The introduction of ─NO 2 groups and ─C(NO 2 ) 2 − in the anions also significantly enhances the density of the salts, thereby improving their detonation performance. A comparison of the detonation velocity and pressure among the various energetic salts revealed that salts A1 ( D = 9.26 km s − 1 , p = 40.2 GPa), A6 ( D = 9.44 km s − 1 , p = 42.47 GPa), B1 ( D = 9.34 km s − 1 , p = 40.57 GPa), and B6 ( D = 9.49 km s − 1 , p = 42.51 GPa) all exhibit detonation velocities and pressures higher than those of the traditional explosive HMX.