Mechanisms and kinetics of the ozonolysis reaction of cis-3-hexenyl acetate and trans-2-hexenyl acetate in atmosphere: a theoretical study

Abstract

Gas-phase reaction mechanisms of ozone with cis/trans-3-hexenyl acetate and cis/trans-2-hexenyl acetate are performed using density functional theory. The reactions are initiated by the formation of the primary ozonides which are followed by the reactions of biradicals with H2O or NO. The formation of the secondary ozonide (SOZ) is also studied. On the basis of the above DFT calculations, the modified multichannel RRKM theory is used to evaluate the rate constants. At 298 K and 101 kPa, the calculated total rate constants are 9.84 × 10−17, 1.39 × 10−17, 2.50 × 10−17, and 7.37 × 10−17 cm3 mol−1 s−1 for cis-3-hexenyl acetate, trans-2-hexenyl acetate, cis-2-hexenyl acetate, and trans-3-hexenyl acetate, respectively. Our results are in good agreement with experimental values. The total rate coefficients are almost pressure-independent in the range of 0.01–10,000 Torr, but show temperature dependence over the whole study range (200–2,000 K). In addition, branching ratios of the favorable reaction channels are obtained.