Theoretical study into effects of different substituents on the structure and properties of Keto-RDX compounds

[Display omitted] •Forty kinds of keto-RDX based derivatives containing different substituents were designed and have been optimized at the B3LYP-D3/6-311G** level.•Horizontal comparison of A and B series derivatives showed that the number of substituents affected the thermal stability of the material.•All the compounds have very high detonation performance, which is better than HMX and RDX. Forty kinds of keto-RDX based derivatives containing different substituents (for instance –NHNH2, -C(NO2)3, –NHNO2, –NO2 and –ONO2) were designed and have been optimized at the B3LYP-D3/6-311G** level. The effects of single and multiple substituents on the properties of these energetic materials were analyzed. The electronic structure, energy gap, heat of formation, detonation performance, thermal stability, thermodynamic parameters and surface electrostatic potential of the compounds were systematically studied. Compared with the traditional energetic compounds HMX (D = 9.10 km s−1, P = 39.0 GPa) and RDX (D = 8.75 km s−1, P = 34.0 GPa), most of the derivatives designed in this paper have higher detonation velocity and detonation pressure. Among them, the largest density, detonation velocity, and detonation pressure are 2.14 g cm−3 (B6), 10.95 km s−1 (D2), and 57.81 GPa (E7), respectively. Combined with surface electrostatic potential analysis, seven keto-RDX based derivatives of C1, C4, C5, E3, E4, E5, and E7 that can be selected as promising high energy density materials were finally picked out.