To design new high-energy density compounds (HEDCs), a series of new bicyclo[2.2.1]heptane derivatives containing an aza
nitrogen atom and nitro substituent were designed and studied theoretically. The density, heat of sublimation and impact
sensitivity were estimated by electrostatic potential analysis of the molecular surface. Based on the designed isodesmic reaction,
and the reliable heat of formation (HOF) of the reference compounds, HOFs were calculated and compared at B3LYP/6-
311G(d,p) and B3P86/6-311G(d,p), respectively. The detonation performances, bond dissociation energies (BDE) and impact
sensitivity were calculated to evaluate the designed compounds. The calculated results show that the number of aza nitrogen
atoms and NO2 groups are two important factors for improving HOF, density and detonation properties. Thermal stability
generally decreases with increasing nitro groups. And the N–NO2 bond is the trigger bond for all designed compounds except
B8, whose trigger bond is C–NO2. Importantly, the BDE values are between 86.95 and 179.71 kJmol−1 and meet the requirement
for HEDCs. Detonation velocity and detonation pressure were found to be 5.77–9.65 km s−1 and 12.30-43.64 GPa, respectively.
After comprehensive consideration of thermal stability, impact sensitivity and detonation properties, A7, A8, B8, C8, D7, E7, F7
and G6 may be considered as potential HEDCs. Especially, A8, B8, C8, and D7 have better detonation properties than the famous
caged nitramine CL-20 (D = 9.40 km/s, P = 42.00GPa). Besides, all the designed potential HEDCs have reasonable impact
sensitivity.

EB00000002801K

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• Computational study of the structure and properties of bicyclo[3.1.1] heptane derivatives for new high-energy density compounds with low impact sensitivity