TY - JOUR
T1 - Gas-phase oxidation of cresol isomers initiated by OH or NO3 radicals in the presence of NO2
AU - Jørgensen, Solvejg
N1 - Special Issue: 7th International Conference on Chemical Kinetics
PY - 2012/3
Y1 - 2012/3
N2 - We have studied the reaction mechanism for both the NO 3- and OH-initiated atmospheric oxidation of three cresol isomers, p-cresol, m-cresol, and o-cresol, in the presence of high NO 2 concentration. We have focused on the reaction mechanism leading to ring-retaining products. Geometries of the reactants, intermediates, transition states, and products have been optimized at DFT-BB1K level of theory with the 6-311+G(d,p) basis set. The single point energy calculations have been carried out at the CCSD(T) level of theory with the cc-pVDZ basis set. Several energetically favorable reaction pathways were revealed for the first time. In the NO 3-initiated reaction, the NO 3 radical is added to the carbon atom with the OH group, then the NO 2 radical is added to one of the neighboring carbon atoms, and finally HNO 3 is eliminated, leading to a methylnitrophenol isomer. In the OH-initiated reaction, the OH radical is added to the carbon atom adjacent to the carbon atom with the OH group; second, the NO 2 radical is added to the carbon atom with the original OH group, and, finally, HNO 2 is eliminated, leading to a dihydroxymethylbenzene isomer. The calculated results were compared with available experimental observations.
AB - We have studied the reaction mechanism for both the NO 3- and OH-initiated atmospheric oxidation of three cresol isomers, p-cresol, m-cresol, and o-cresol, in the presence of high NO 2 concentration. We have focused on the reaction mechanism leading to ring-retaining products. Geometries of the reactants, intermediates, transition states, and products have been optimized at DFT-BB1K level of theory with the 6-311+G(d,p) basis set. The single point energy calculations have been carried out at the CCSD(T) level of theory with the cc-pVDZ basis set. Several energetically favorable reaction pathways were revealed for the first time. In the NO 3-initiated reaction, the NO 3 radical is added to the carbon atom with the OH group, then the NO 2 radical is added to one of the neighboring carbon atoms, and finally HNO 3 is eliminated, leading to a methylnitrophenol isomer. In the OH-initiated reaction, the OH radical is added to the carbon atom adjacent to the carbon atom with the OH group; second, the NO 2 radical is added to the carbon atom with the original OH group, and, finally, HNO 2 is eliminated, leading to a dihydroxymethylbenzene isomer. The calculated results were compared with available experimental observations.
U2 - 10.1002/kin.20703
DO - 10.1002/kin.20703
M3 - Journal article
SN - 0538-8066
VL - 44
SP - 165
EP - 178
JO - International Journal of Chemical Kinetics
JF - International Journal of Chemical Kinetics
IS - 3
ER -