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

CD Daub and R Valiev and VT Salo and I Zakai and RB Gerber and T Kurten, ACS EARTH AND SPACE CHEMISTRY, 6, 2446-2452 (2022).

DOI: 10.1021/acsearthspacechem.2c00159

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

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