Termolecular chemistry facilitated by radical-radical recombinations and its impact on flame speed predictions

Recent theoretical studies have shown that termolecular chemistry can be facilitated through reactions of flame radicals (H, O, and OH) or O₂ with highly-energized collision complexes (either radical or stable species) formed in exothermic reactions. In this work, radical-radical recombination reaction induced termolecular chemistry and its impact on combustion modeling was studied. Two recombination reactions, H + CH₃ + M → CH₄ + M and H + OH + M → H₂O + M, were analyzed using ab-initio master equation analyses guided by quasiclassical trajectory results. The dynamics results and the master equation calculations indicate that CH₄^? and H₂O^? (formed in the two radical-radical reactions outlined above) react rapidly with flame radicals and O₂ at rates that are competitive with collisional cooling. The addition of these processes into conventional combustion modeling requires two modifications: the inclusion of the new nonthermal termolecular reaction rates and the simultaneous reduction of the competing recombination reaction rates. The former is described with newly derived Arrhenius expressions based on quasiclassical trajectories, and the latter is achieved by perturbing the recombination reaction rate during the simulation. Kinetic modeling was used to gauge the impact of including this nonthermal chemistry for H₂/CH₄-air laminar flames speeds. Inclusion of this nonthermal chemistry has a noticeable impact on simulated flame speeds. The procedure developed here can be utilized to properly quantify the effects of such nonthermal reactions in macroscopic kinetic models.