Atmospheric oxidation mechanism of toluene.

The atmospheric oxidation mechanism of toluene initiated by OH radical addition is investigated by quantum chemistry calculations at M06-2X, G3MP2-RAD, and ROCBS-QB3 levels and by kinetics calculation by using transition state theory and unimolecular reaction theory coupled with master equation (RRKM-ME). The predicted branching ratios are 0.15, 0.59, 0.05, and 0.14 for OH additions to ipso, ortho, meta, and para positions (forming R1-R4 adducts), respectively. The fate of R2, R4, and R1 is investigated in detail. In the atmosphere, R2 reacts with O2 either by irreversible H-abstraction to form o-cresol (36%), or by reversible recombination to R2-1OO-syn and R2-3OO-syn, which subsequently cyclize to bicyclic radical R2-13OO-syn (64%). Similarly, R4 reacts with O2 with branching ratios of 61% for p-cresol and 39% for R4-35OO-syn, while reaction of R1 and O2 leads to R1-26OO-syn. RRKM-ME calculations show that the reactions of R2/R4 with O2 have reached their high-pressure limits at 760 Torr and the formation of R2-16O-3O-s is only important at low pressure, i.e., 5.4% at 100 Torr. The bicyclic radicals (R2-13OO-syn, R4-35OO-syn, and R1-26OO-syn) will recombine with O2 to produce bicyclic alkoxy radicals after reacting with NO. The bicyclic alkoxy radicals would break the ring to form products methylglyoxal/glyoxal (MGLY/GLY) and their corresponding coproducts butenedial/methyl-substituted butenedial as proposed in earlier studies. However, a new reaction pathway is found for the bicyclic alkoxy radicals, leading to products MGLY/GLY and 2,3-epoxybutandial/2-methyl-2,3-epoxybutandial. A new mechanism is proposed for the atmospheric oxidation mechanism of toluene based on current theoretical and previous theoretical and experimental results. The new mechanism predicts much lower yield of GLY and much higher yield of butenedial than other atmospheric models and recent experimental measurements. The new mechanism calls for detection of proposed products 2,3-epoxybutandial and 2-methyl-2,3-epoxybutandial.