Mechanism and Kinetics for the Initial Steps of Pyrolysis and Combustion of 1,6-Dicyclopropane-2,4-hexyne from ReaxFF Reactive Dynamics

We report the kinetic analysis and mechanism for the initial steps of pyrolysis and combustion of a new fuel material, 1,6-dicyclopropane-2,4-hexyne, that has enormous heats of pyrolysis and combustion, making it a potential high-energy fuel or fuel additive. These studies employ the ReaxFF force field for reactive dynamics (RD) simulations of both pyrolysis and combustion processes for both unimolecular and multimolecular systems. We find that both pyrolysis and combustion initiate from unimolecular reactions, with entropy-driven reactions being most important in both processes. Pyrolysis initiates with extrusion of an ethylene molecule from the fuel molecule and is followed quickly by isomerization of the fuel molecule, which induces additional radicals that accelerate the pyrolysis process. In the combustion process, we find three distinct mechanisms for the O2 attack on the fuel molecule: (1) attack on the cyclopropane, ring expanding to form the cyclic peroxide which then decomposes; (2) attack onto the central single bond of the diyne which then fissions to form two C_5H_5O radicals; (3) attack on the alkyne-cyclopropane moiety to form a seven-membered ring peroxide which then decomposes. Each of these unimolecular combustion processes releases energy that induces additional radicals to accelerate the combustion process. Here oxygen has major effects both as the radical acceptor and as the radical producer. We extract both the effective activation energy and the effective pre-exponential factor by kinetic analysis of pyrolysis and combustion from these ReaxFF simulations. The low value of the derived effective activation energy (26.18 kcal/mol for pyrolysis and 16.40 kcal/mol for combustion) reveals the high activity of this fuel molecule