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

Abstract

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.