A DFT theoretical study of heats of formation and detonation properties of nitrogen-rich explosives

We present density-functional theory predictions and analysis of some properties of synthesized high-nitrogen compounds 3,6-diazido-1,2,4,5-tetrazine (DiAT) and N-oxides of 3,3′-azo-bis(6-amino-1,2,4,5-tetrazine) (DAATO) together with 3,6-di(hydrazino)-1,2,4,5-tetrazine (DHT) and 3,3′-azo-bis(6-amino-1,2,4,5-tetrazine) (DAAT) for which experimental data are available. In this work the reference molecules DHT and DAAT have been studied in order to validate the theoretical approach and facilitate further progress developments for the molecules of interest such as DiAT and DAATO. Geometries of all compounds have been optimized employing the B3LYP density-functional method in conjunction with 6-311++G(3d,3p) basis sets. The energy content of the molecules in the gas phase is evaluated by calculating standard enthalpies of formation, using isodesmic reaction paths. We also include estimates of the condensed-phase heats of formation and heats of sublimation in the framework of the Politzer approach. The obtained results show that DiAT compound has the highest heat of formation (231 kcal/mol) in comparison with those of DHT, DAAT and DAATO molecules. The detonation velocity and pressure have also been estimated for these molecules using the Stine method.