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.