Theoretical studies of high-nitrogen-containing energetic compounds based on the s-tetrazine unit

In order to develop new high-energy-density materials (HEDMs), we have investigated 12 substituted s-tetrazine (TZ) compounds, where s-tetrazine was substituted by amino, amido and related groups. Density functional theory (DFT) was used to predict the optimized geometries, electronic structures, total energy, heats of formation (HOFs) and densities. In addition the detonation properties were evaluated by using the VLW equation of state (EOS). The standard enthalpy of formation, the Gibbs free energy, entropy and equilibrium constants were used to estimate the success of the synthetic substitution reactions, which provided theoretical support for practical work. The bond dissociation energy (BDE) of bond C-R was calculated at each stage of the substitution reaction. The calculated results showed that substitution of amino, amido and their derivatives in the TZ ring enhances the HOF values and is favorable for increasing the thermal stability. The calculated detonation properties indicated that incorporating the above groups into the TZ ring is beneficial for improving the explosive performance. Considering the detonation properties and thermal stability, the 12 derivatives may be regarded as promising candidates as high-energy-density materials (HEDMs).