A DFT study of cage compounds: 3, 5, 8, 10, 11, 12-hexanitro-3, 5, 8, 10, 11, 12-hexaazatetracyclo [5.5.1.1~(2,6).0~(4,9)] dodecane and its derivatives as high energetic materials

摘要

A new cage compound, 3, 5, 8, 10, 11, 12-hexanitro-3, 5, 8, 10, 11, 12-hexaazatetracyclo [5.5.1.12,6.04,9] dodecane (HNHATCD, I) as well as its -ONO_2 (II) and -N_3 (III) derivatives were proposed in the present work. Their molecular structures were optimized at the B3LYP/6-31G(d,p) level of density functional theory. Heat of formation, strain energy, detonation performance, and thermal stability were studied. Results show that the -N_3 group greatly increases the heat of formation, but decreases the strain energy and density, and it is much more helpful for enhancing the detonation energy than the -NO_2 and -ONO_2 groups. An analysis of bond dissociation energies (BDEs) of the weakest bonds implies that the BDE of -N_3 derivatives is the smallest but it is still larger than 120 kJ mol~(-1), revealing that these designed compounds have a high thermal stability. Considering the detonation performance and thermal stability, I and II may be potential candidates of high energy density materials.