Density functional theory has been employed to study the structures and properties of polynitrotetrahedranes at the B3LYP/6-31G** level. Based on the fully optimized structures, their infrared spectra and thermodynamic properties were calculated. By designing isodesmic reactions, their gas heats of formation were evaluated. Their detonation properties (detonation velocity D and detonation pressure p) were obtained from the Kamlet-Jacobs equations. Their trigger bond and thermal stability were confirmed by comparing the bond dissociation energies of C—C (EC—C) and C—N (EC—N). The relationship between the structures and properties of these compounds was discussed. Considering the criterion as a high energy density compound (HEDC), no polynitrotetrahedrane was finally recommended as a potential HEDC.

Key words: polynitrotetrahedrane, density functional theory, isodesmic reaction, detonation property, pyrolysis mechanism