Exploration of High‐Energy‐Density Materials: Computational Insight into Energetic Derivatives Based on 1,2,4,5‐Tetrahydro‐1,2,4,5‐tetrazine

Density functional theory was employed to investigate ten 1,2,4,5‐tetrahydro‐1,2,4,5‐tetrazine‐based energetic materials. The heats of formation and detonation properties were calculated by isodesmic reactions and Kamlet–Jacobs equations. The thermal stabilities and impact sensitivities were also estimated to give a better understanding of their decomposition mechanism. The results indicate that all of the designed compounds have high positive heats of formation ranging from 525.1 to 1639.1 kJ mol(−1), moderate detonation properties (heats of detonation of 536.6 to 2187.6 cal g(−1), theoretical densities of 1.48 to 2.32 g cm(−3), detonation velocities of 7.02 to 12.18 km s(−1), and detonation pressures of 19.8 to 75.1 GPa), and acceptable stabilities (bond dissociation energies of 0.8 to 104.9 kJ mol(−1)). Taking both the detonation properties and the stabilities into consideration, compounds A4 and B4 were finally selected as promising candidates of high‐energy‐density materials, as their detonation properties and impact sensitivities were superior to those of HMX. Additionally, the frontier molecular orbitals, electronic densities, electrostatic potentials, and thermal dynamic parameters of compounds A4 and B4 were also investigated.