Comparing Reaction Routes for ³(RO···OR') Intermediates Formed in Peroxy Radical Self- and Cross-Reactions

Organic peroxy radicals (RO₂) are key intermediates in the chemistry of the atmosphere. One of the main sink reactions of RO₂ is the recombination reaction RO₂ + R'O₂, which has three main channels (all with O₂ as a coproduct): (1) R_-H═O + R'OH, (2) RO + R'O, and (3) ROOR'. The RO + R'O "alkoxy" channel promotes radical and oxidant recycling, while the ROOR' "dimer" channel leads to low-volatility products relevant to aerosol processes. The ROOR' channel has only recently been discovered to play a role in the gas phase. Recent computational studies indicate that all of these channels first go through an intermediate complex ¹(RO···³O₂···OR'). Here, ³O₂ is very weakly bound and will likely evaporate from the system, giving a triplet cluster of two alkoxy radicals: ³(RO···OR'). In this study, we systematically investigate the three reaction channels for an atmospherically representative set of RO + R'O radicals formed in the corresponding RO₂ + R'O₂ reaction. First, we systematically sample the possible conformations of the RO···OR' clusters on the triplet potential energy surface. Next, we compute energetic parameters and attempt to estimate reaction rate coefficients for the three channels: evaporation/dissociation to RO + R'O, a hydrogen shift leading to the formation of R'_-H═O + ROH, and "spin-flip" (intersystem crossing) leading to, or at least allowing, the formation of ROOR' dimers. While large uncertainties in the computed energetics prevent a quantitative comparison of reaction rates, all three channels were found to be very fast (with typical rates greater than 10⁶ s^-1). This qualitatively demonstrates that the computationally proposed novel RO₂ + R'O₂ reaction mechanism is compatible with experimental data showing non-negligible branching ratios for all three channels, at least for sufficiently complex RO₂.