Abstract
Organic peroxy radicals (RO(2)) are key intermediates in atmospheric chemistry and can undergo a large variety of both uni- and bimolecular reactions. One of the least understood reaction classes of RO(2) are their self- and cross-reactions: RO(2) + R'O(2). In our previous work, we have investigated how RO(2) + R'O(2) reactions can lead to the formation of ROOR' accretion products through intersystem crossings and subsequent recombination of a triplet intermediate complex (3)(RO···OR'). Accretion products can potentially have very low saturation vapor pressures, and may therefore participate in the formation of aerosol particles. In this work, we investigate the competing H-shift channel, which leads to the formation of more volatile carbonyl and alcohol products. This is one of the main, and sometimes the dominant, RO(2) + R'O(2) reaction channels for small RO(2). We investigate how substituents (R and R' groups) affect the H-shift barriers and rates for a set of (3)(RO···OR') complexes. The variation in barrier heights and rates is found to be surprisingly small, and most computed H-shift rates are fast: around 10(8)-10(9) s(-1). We find that the barrier height is affected by three competing factors: (1) the weakening of the breaking C-H bond due to interactions with adjacent functional groups; (2) the overall binding energy of the (3)(RO···OR'), which tends to increase the barrier height; and (3) the thermodynamic stability of the reaction products. We also calculated intersystem crossing rate coefficients (ISC) for the same systems and found that most of them were of the same order of magnitude as the H-shift rates. This suggests that both studied channels are competitive for small and medium-sized RO(2). However, for complex enough R or R' groups, the binding energy effect may render the H-shift channel uncompetitive with intersystem crossings (and thus ROOR' formation), as the rate of the latter, while variable, seems to be largely independent of system size. This may help explain the experimental observation that accretion product formation becomes highly effective for large and multifunctional RO(2).