Substituent effects on the properties related to detonation performance and stability for pentaprismane derivatives

Density functional theory calculations were used to study energetic and stability properties for a series of pentaprismane (C₁₀H₁₀) derivatives with different substituent groups (NO₂, NO, CN, N₃, NH₂, NHNO₂, and ONO₂). The results indicated that the N₃ and CN groups greatly increase while the ONO₂ group decreases the heats of formation. Moreover, the NO₂, NHNO₂, and ONO₂ derivatives possess better detonation properties (detonation velocities = 8.92–9.72 km s⁻¹ and detonation pressures = 38.37–45.24 GPa) than those of other derivatives due to high densities (1.97–2.08 g cm⁻³) and large heats of detonation (1189.22–1807.45 kJ mol⁻¹). An analysis of the bond dissociation energies (BDE) revealed that all investigated compounds meet the qualification of energetic material (BDE > 84 kJ mol⁻¹) even though the initiation decomposition steps are diverse (breaking of C–C bonds for NO₂, N₃, NH₂, and CN derivatives, N–NO₂ bond for NHNO₂ derivative, O–NO₂ bond for ONO₂ derivative, and cage–NO bond for NO derivative). Considering both detonation performance and thermal stability, NO₂ and NHNO₂ derivatives are proposed to be potential candidates of high energy density materials.