Novel fluorine-containing energetic materials: how potential are they? A computational study of detonation performance

High-energy density materials (HEDMs) have emerged as a research focus due to their advantageous ultra-high detonation performance and better sensitivity. The primary aim of this study revolves around crafting HEDMs that strike a delicate balance between exceptional performance and minimal sensitivity. Density functional theory (DFT) was utilized to evaluate the geometric structures, energies, densities, energy properties, and sensitivities of 39 designed derivatives. The theoretical density (ρ) and heat of formation (HOF) were used to estimate the detonation velocity (D) and pressure (P) of the title compounds. Our study shows that the introduction of fluorine-containing substituents or fluorine-free substituents into the CHOFN backbone or the CHON backbone can significantly enhance the detonation performance of derivatives. Derivative B1 exhibits the better overall performance, including superior density, detonation performance, and sensitivity (P = 58.89 GPa, D = 8.02 km/s, ρ = 1.93 g/cm3, and characteristic height H50 = 34.6 cm). Our molecular design strategy contributes to the development of more novel HEDMs with excellent detonation performance and stability. It also marks a significant step towards a material engineering era guided by theory-based rational design.GaussView 6.0 was used for construction of molecular system coordinates, and Gaussian 16 was used to obtain optimal structures, energies, and volumes of all compounds at the B3LYP/6-31+G(d,p) level of theory. It was characterized to be the local energy minimum on the potential energy surface without imaginary frequencies at the same theory level. Molecular weight, isosurface area, and overall variance were obtained using the Multiwfn 3.3. The detonation properties of the materials were analyzed using the C-J thermodynamic detonation theory. Our broad analysis facilitated an extensive assessment of these properties.