Secondary decomposition reactions in nitramines

Thermal decomposition of nitramines is known to proceed via multiple, competing reaction branches [1], some of which are triggered by secondary reactions between initial decomposition products and unreacted nitramine molecules. Better mechanistic understanding of these secondary reactions is needed to enable extrapolations of measured rates to higher temperatures and pressures relevant to shock ignition. I will present density functional theory (DFT) based simulations of nitramines that aim to re-evaluate known elementary mechanisms [2,3] and seek alternative pathways in the gas and condensed phases. [1] S. Maharrey and R. Behrens, J. Phys. Chem. A, 109, 11236 (2005) [2] C. F. Melius and M. C. Piqueras, P. Combust. Inst., 29, 2863 (2002) [3] K. Irikura, J. Phys. Chem. A, 117, 2233 (2013)