High-Energy Nitramine Explosives: A Design Strategy from Linear to Cyclic to Caged Molecules.

After carefully analyzing the Kamlet-Jacobs (K-J) equations and the structural traits of well-known explosives, hexahydro-1,3,5-trinitro-1,3,5-triazin (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and hexanitrohexaazaisowurtizitane (CL-20), diverse nitramine explosives including linear (Models IA, IB, and IC), cyclic (Model II), and caged (Models IIIA and IIIB) molecules were designed by incorporating various number () of -CHNNO- structural unit and studied using the B3LYP/6-31G* and B3PW91/6-31G** methods of the density functional theory. Computational results show that all of the energetic parameters, that is, density (ρ), detonation velocity (), and detonation pressure (), follow the order of IIIB > IIIA > II > IA > IB > IC. With the increasing , the and of linear nitramines eventually keep stable. This clearly indicates that elongating the chain length (e.g., polymerization) brings little or even negative benefit in boosting the explosive properties. The oxygen balance and the K-J equation parameter ϕ both have a significant influence on the detonation properties. Caged compound IIIA2 has not only comparable energetic properties but also better sensitivity and thermal stability than CL-20.