Computational studies on the infrared vibrational spectra, thermodynamic properties, detonation properties, and pyrolysis mechanism of octanitrocubane

Abstract

The molecular geometries, infrared vibrational spectra, and thermodynamic properties of octanitrocubane (ONC) are calculated using the density functional theory (DFT) method at the B3LYP/6-31G* level. The IR frequency scaling factor 0.9501 suitable for polynitrocubanes is obtained at the B3LYP/6-31G* level, and the calculated IR frequencies of ONC are scaled. The accurate heat of formation 726.47 kJ/mol of ONC in gas phase is obtained via designed isodesmic reaction in which the cubane cage skeleton has been kept. The sublimation enthalpy, density, and heat of formation for ONC crystal are also calculated, and they are 220.63 kJ/mol, 2.189 g/cm3, and 505.84 kJ/mol, respectively. In addition, the estimated detonation velocity and detonation pressure of ONC are 10.26 mm/ms and 520.86 kbar, respectively. Finally, the pyrolysis mechanism of ONC is studied using various theoretical methods, i.e., MP2, DFT, and selected MINDO/3 semiempirical MO, based on the unrestricted Hartree–Fock model. The calculated results show that the pyrolysis initiation reaction of ONC, i.e., rate-controlling step, is to form a diradical by the single C–C bond breaking in the cube. The second C–C bond breaking is easily followed to form a nitrocyclooctatetraene. The calculated activation energy for the pyrolysis initiation reaction of ONC, obtained from B3LYP/6-31G* method, is 155.30 kJ/mol, which this rather large activation energy indicates that ONC is a new type of energetic material with less sensitivity and better thermal stability, and has highly exploitable values.