DFT studies on nitrogen-rich pyrazino [2, 3-e] [1, 2, 3, 4] tetrazine-based high-energy density compounds

By using the density functional theory method, we investigated the heats of formation (HOFs), electronic structure, detonation properties, thermal stability and sensitivity for a set of pyrazino [2, 3-e] [1, 2, 3, 4] tetrazine derivatives with different substituents and different numbers of N-oxides. Our findings reveal that the HOFs of the derivatives decrease dramatically with the increasing number of N-oxides. The effects of the substituents on the HOMO-LUMO gaps are coupled with those of the N-oxides. The calculated detonation properties point out that -NF₂, -ONO₂ and an increasing number of N-oxides are very helpful for improving the detonation performance of the designed derivatives. The bond dissociation energies of the weakest bonds indicate that a majority of our designed compounds have better thermal stability. The -NH₂ group is very useful to decrease the free space value. Most of the derivatives have higher h₅₀ values compared with parent molecules. Considering the sensitivity, thermal stability and detonation performance, four compounds could be considered as potential candidates of high-energy density compounds.