The paper concentrates on the "molecular design" of 1,3-bishomopentaprismine (BPP) derivatives with CN, NC, and ONO2 groups as high energy density compounds (HEDCs). The heats of formation (HOFs), densities (rho), detonation velocities (D), and pressures (P) for a series of BPP derivatives, as well as their thermal stabilities, were calculated using density functional theory. The HOFs are high and increase with the substituted number (n) for BPP derivatives with CN and NC groups while are low and decrease with n for derivatives with ONO2 group. D and P were estimated by using modified Kamlet-Jacobs equations based on the calculated HOFs and rho. The BPP derivatives with ONO2 groups have excellent energetic properties to be HEDCs while the other two kinds of derivatives have relatively low rho, D, and P, revealing that CN and NC groups are not ideal substituents in the construction of HEDCs. The trigger bond in the pyrolysis process for CN and NC derivatives is the C-C bond in the skeleton, and these derivatives all have good thermal stability. In comparison, the trigger bond in the pyrolysis process for ONO2 derivatives is the O-NO2 bond, and these compounds are medium-stable. Taking both energetic properties and thermal stability into account, BPP derivatives with 6-8 ONO2 groups are recommended as potential candidates of HEM. These results would provide basic information for the further studies of the title compounds,