Theoretical study on the formation of Criegee intermediates from ozonolysis of pentenal: An example of trans-2-pentenal.

Abstract

In this study, we investigated the reaction mechanism and kinetics of ozone with trans-2-pentenal using density functional theory (DFT) and conventional transition state theory (CTST). At 298K and 1atm, the gas-phase reaction mechanisms and kinetic parameters were calculated at the level of CCSD(T)/6-311+G(d,p)//M06-2X/6-311+G(d,p). Both CC and CO bond cycloaddition as well as hydrogen abstraction were found. The calculations indicated that the main reaction path is 1,3-dipole cycloaddition reactions of ozone with CC bond with the relatively lower syn-energy-barrier of 3.35kcalmol-1 to form primary ozonide which decomposed to produce a carbonyl oxide called a Criegee intermediate (CI) and an aldehyde. The subsequent reactions of CIs were analysed in detail. It is found that the reaction pathways of the novelty CIs containing an aldehyde group are extremely similar with general CIs when they react with NO, NO2, SO2, H2O, CH2O and O2. The condensed Fukui function were calculated to identify the active site of the chosen molecules. At 298K and 1atm, the reaction rate coefficient was 9.13×10-18cm3 molecule-1 s-1 with atmospheric lifetime of 1.3 days. The calculated rate constant is in general agreement with the available experimental data. The branching ratios indicated that syn-addition pathways are prior to anti-addition. The atmospheric ratios for CIs formation and the bimolecular reaction rate constants for the Criegee intermediates with the variety of partners were calculated. Our theoretical results are of importance in atmospheric chemistry of unsaturated aldehyde oxidation by ozone.