Computational Study of the 1,3-Dipolar Cycloaddition between Criegee Intermediates and Linalool: Atmospheric Implications

Abstract

In this research, we investigated the essential role of biogenic volatile organic compound emissions in regulating tropospheric ozone levels, atmospheric chemistry, and climate dynamics. We explored linalool ozonolysis and secondary organic aerosol formation mechanisms, providing key insights into atmospheric processes. Computational techniques, such as density functional theory calculations and molecular dynamics simulations, were employed for the analysis. Our study delves into the energetic and mechanistic aspects of the 1,3-dipolar cycloadditions involving linalool and its ozonolysis byproducts, known as Criegee intermediates. A total of 24 reactions were analyzed from the three possible Criegee intermediates formed, resulting from different reactant orientations and their endo/exo isomers. We found that only four of these reactions exhibit large rate constants that can compete with tropospheric reactions. This reactivity pattern was characterized by analyzing reactivity indices from conceptual density functional theory and determining that electron flux originates from linalool to the Criegee intermediates. Greater electrophilicity in the Criegee intermediates results in a lower reaction activation energy, confirmed by the global electrophilicity index. Furthermore, using the activation strain model and energy decomposition analysis, we found that differences in activation energies were primarily driven by nonorbital energy factors. Finally, molecular dynamics simulations showed that the final cycloaddition adducts of the most favorable 1,3-dipolar cycloaddition interact favorably with water molecules in an exergonic process, adsorbing up to 92% of the water molecules after 20 ns. Our findings provide insights that enhance our understanding of the interactions between natural emissions and atmospheric constituents.