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.

Interest in peroxy radicals derives from their central role in tropospheric and low-temperature combustion processes; however, their transient nature limits the scope of possible experimental characterization. As a result, theoretical methods (notably, coupled-cluster theory) have become indispensable in the reliable prediction of properties of such ephemeral open-shell systems. Herein, the X[combining tilde] and à state conformers of ethylperoxy radical (CHO) have been structurally optimized at the CCSD(T)/ANO2 level of theory. Relative enthalpies at 0 K [including à ← X[combining tilde] transition origins (T)] are reported, incorporating CCSD(T) electronic energies extrapolated to the complete basis set limit via the focal point approach. Higher-level computations, employing basis sets as large as cc-pV5Z and post-HF methods up to CCSDT(Q), prove essential in achieving predictions to within 10 cm for experimental T; we predict 7363 and 7583 cm for the trans and gauche conformers, respectively. Furthermore, predictions of X[combining tilde] state fundamental transitions incorporating CCSD(T)/ANO0 anharmonic contributions are given. For each conformer, all 21 modes were characterized, improving upon the 16 modes reported in the experimental literature, and providing predictions for the 5 remaining modes.