Computed Pre-reactive Complex Association Lifetimes Explain Trends in Experimental Reaction Rates for Peroxy Radical Recombinations

The lifetimes of pre-reactive complexes, although implicitly part the equations used to model many gas-phase bimolecular reactions, have seldom been included in quantitative calculations rate coefficients. Here, we demonstrate application empirical molecular dynamics simulations collisions between peroxy radicals association lifetimes. With exception methyl peroxy–acetyl system, measurements based on a phenomenological are shown correlate well with available experimental data for recombination reactions cases where rate-limiting transition state lies below reactants energy. Further, predict reaction rates larger α-pinene-derived radicals, and interpret our results tandem these systems, which great relevance improve understanding atmospheric aerosol formation.