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'O-2, which has three main channels (all with O-2 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 center dot center dot center dot O-3(2)center dot center dot center dot OR'). Here, O-3(2) is very weakly bound and will likely evaporate from the system, giving a triplet cluster of two alkoxy radicals: (3)(RO center dot center dot center dot 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'O-2 reaction. First, we systematically sample the possible conformations of the RO center dot center dot center dot 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 10 6 s(-1)). This qualitatively demonstrates that the computationally proposed novel RO2 + R'O-2 reaction mechanism is compatible with experimental data showing non-negligible branching ratios for all three channels, at least for sufficiently complex RO2.