B3LYP/aug-cc-pvDZ level of theory is applied to study the geometries, bond dissociation energies and properties of energetic material of 1,2,4,5-tetrazine derivatives in which hydrogen atoms of 1,2,4,5- tetrazine have been substituted by CN, NO₂, NH₂, N₃, N₂H, NHNH₂, N₄H and N₄H₃ groups. Compared with the parent molecule unsubstituted, derivative substituted by CN group results in higher bond dissociation energies, whereas the other lead to lower ones. The studies indicated that the higher heats of formation of compounds of substituent groups possess, the higher ones of derivatives. The normalized heats of formation of these derivatives substituted by N₃, N₂H and NHNH₂ are 83.1～95.2 kJ, which is higher than that of triazido-s-triazine (70.2 kJ) reported. For derivatives substituted by N₄H, N₃, N₄H₃, N₂H and CN groups, heats of formation calculated lie in the range of 904.9～1496.6 kJ•mol^－1, but derivatives substituted by N₄H and N₄H₃ show low dissociation energies and relatively low stability.

Key words: high energy density material, 1,2,4,5-tetrazine, substitutent groups containing nitrogen, dissociation energy, heat of formation