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Gas‐phase oxidation of cresol isomers initiated by OH or NO 3 radicals in the presence of NO 2
Author(s) -
Jørgensen Solvejg
Publication year - 2012
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20703
Subject(s) - chemistry , radical , transition state , basis set , reaction mechanism , carbon atom , cresol , carbon fibers , medicinal chemistry , atom (system on chip) , ring (chemistry) , p cresol , transition state theory , photochemistry , computational chemistry , kinetics , density functional theory , reaction rate constant , organic chemistry , catalysis , phenol , materials science , physics , quantum mechanics , composite number , computer science , composite material , embedded system
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. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 165–178, 2012