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

Research output: Contribution to journalArticleScientificpeer-review

Abstract

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 α-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.
Original languageEnglish
JournalACS Earth and Space Chemistry
Volume6
Pages (from-to)2446-2452
Number of pages7
ISSN2472-3452
DOIs
Publication statusPublished - 16 Sep 2022
MoE publication typeA1 Journal article-refereed

Fields of Science

  • peroxy radicals
  • aerosol
  • reaction kinetics
  • Arrhenius equation
  • ?-pinene
  • CRIEGEE INTERMEDIATE CH2OO
  • SELF-REACTION
  • TROPOSPHERIC DEGRADATION
  • ALPHA-PINENE
  • FORCE-FIELD
  • MECHANISM
  • OZONOLYSIS
  • OXIDATION
  • PROTOCOL
  • 116 Chemical sciences

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