Increasing Oxygen Balance Leads to Enhanced Performance in Environmentally Acceptable High-Energy Density Materials: Predictions from First-Principles Molecular Dynamics Simulations.

Environmental concerns have stimulated the development of green alternatives to environmentally pollutive nitramine compounds used for high-energy density materials (HEDMs). The excellent energetic properties of CL20 make it a promising candidate, but its negative oxygen balance limits its efficiency for industrial and military applications. We predict here that CL20-EO formed by introducing ether links into the CC bonds of the original CL20 structure to attain balanced CO 2 and H 2 O production leads to improved performance while minimizing the formation of carbonaceous clusters and toxic gases. To test this concept, we predicted the detonation properties at the Chapman-Jouguet (CJ) state using reactive molecular dynamics simulations with the ReaxFF force field combined with quantum mechanics based moleculear dynamics. We predict that CL20-EO enhances energetic performance compared to CL20 with a 6.0% increase in the CJ pressure and a 1.1% increase in the detonation velocity, which we attribute to achieving the correct oxygen balance to produce fully oxidized gaseous products. After expansion to normal conditions from the CJ state, CL20-EO leads only to nontoxic fully oxidized gases instead of forming the carbonaceous clusters and toxic gases found with CL-20. Thus, CL20-EO is predicted to be environmentally green. These results indicate that oxygen balance plays an important role in both energy availability and end-product toxicity and that balanced CO 2 and H 2 O production systems provide promising candidates for the next generation of environmentally acceptable alternatives to toxic HEDMs while also enhancing the detonation performance.