Theoretical Study on Thermodynamic and Detonation Properties of Polynitrocubanes

We investigated the heat of formation (Δ_fH) of polynitrocubanes using density functional theory B3LYP and HF methods with 6‐31G*, 6‐311+G**, and cc‐pVDZ basis sets. The results indicate that Δ_fH firstly decreases (nitro number m=0–2) and then increases (m=4–8) with each additional nitro group being introduced to the cubane skeleton. Δ_fH of octanitrocubane is predicted to be 808.08 kJ mol⁻¹ at the B3LYP/6‐311+G** level. The Gibbs free energy of formation (Δ_fG) increases by about 40–60 kJ mol⁻¹ with each nitro group being added to the cubane when the substituent number is fewer than 4, then Δ_fG increases by about 100–110 kJ mol⁻¹ with each additional group being attached to the cubic skeleton. Both the detonation velocity and the pressure for polynitrocubanes increase as the number of substituents increases. Detonation velocity and pressure of octanitrocubane are substantially larger than the famous widely used explosive cyclotetramethylenetetranitramine (HMX).