Exploring mechanisms of a tropospheric archetype: CH3O2 + NO

Methylperoxy radical (CH3O2) and nitric oxide (NO) contribute to the propagation of photochemical smog in the troposphere via the production of methoxy radical (CH3O) and nitrogen dioxide (NO2). This reaction system also furnishes trace quantities of methyl nitrate (CH3ONO2), a sink for reactive NOx species. Here, the CH3O2 + NO reaction is examined with highly reliable coupled-cluster methods. Specifically, equilibrium geometries for the reactants, products, intermediates, and transition states of the ground-state potential energy surface are characterized. Relative reaction enthalpies at 0 K (ΔH0K) are reported; these values are comprised of electronic energies extrapolated to the complete basis set limit of CCSDT(Q) and zero-point vibrational energies computed at CCSD(T)/cc-pVTZ. A two-part mechanism involving CH3O and NO2 production followed by radical recombination to CH3ONO2 is determined to be the primary channel for formation of CH3ONO2 under tropospheric conditions. Constrained optimizations of the reaction paths at CCSD(T)/cc-pVTZ suggest that the homolytic bond dissociations involved in this reaction path are barrierless.