Theoretical investigation on the mechanism and kinetics of the OH•‒initiated atmospheric degradation of p-chloroaniline: Addition of [formula omitted] and isomerization of peroxy radicals

Abstract

Atmospheric oxidation of the p-chloroaniline-OH• adduct [C6H4ClNH2–OH]• (AD-C2) by ∑g−3O2 and internal isomerization processes of peroxy radical [C6H4ClNH2–OH]•-O2 are theoretically investigated at the M06-2X/aug-cc-pVTZ and CBS-QB3//M06-2X/aug-cc-pVTZ level of theories. Potential energy surfaces (PESs) for the most efficient pathways indicated that the oxidation process begins via the complexation of individual reactants in syn mode forming PRCy-iOO-syn (y = 2,5) in an exothermic and endogenic step. The syn mode addition is favored over the anti one due to the formation of internal hydrogen bond between the hydroxyl and peroxy groups. Formation of new C5–OO bond in PRCy-iOO-syn complex is an unimolecular process which is exothermic and exoergic. This pathway is predominated over other internal conversions due to the presence of stronger intramolecular hydrogen bond. Cyclization of the produced [C6H4ClNH2–OH]•-O2 peroxy radical AD-C2-5OO-syn into the bicyclic peroxy radical AD-C2-5,6OO-syn is the last step which is strongly endothermic and endogenic. The rate coefficients are calculated by means of the RRKM theory over the temperature range 250–350 K and at a pressure range of 0.1 bar to the high-pressure limit. The RRKM rate coefficients at the M06-2X/aug-cc-pVTZ level for the first bimolecular and last unimolecular steps are in order of 10−16 cm3 molecule−1 s−1 and 10−7 s−1, respectively, while the obtained rate coefficients at the CBS-QB3//M06-2X/aug-cc-pVTZ are overestimated about two order of magnitude.