Molecular design of energetic bicyclo-HMX derivatives: insights from density functional theory

Three new bicyclo-HMX (2, 4, 6, 8-tetranitro-1H, 5H-2, 4, 6, 8-tetraaza-bicyclo [3. 3. 0] octane) derivatives have been designed and calculated at the density functional theory (DFT)-B3LYP/6-311 G (d, p) level. Detonation performance was evaluated by Kamlet-Jacobs (K-J) equations based on the theoretical crystal densities and condensed-phase heats of formation. Sensitivity was evaluated using the frontier orbital energies and characteristic heights (h₅₀). The predicted theoretical crystal densities of the derivatives were above 1.90 g · cm^-3, detonation velocities were over 9.0 km · s^-1, and detonation pressures were about 40 GPa, showing that bicyclo-HMX derivatives may be the potential high energetic density materials (HEDMs). (authors)