Abstract: The mechanisms of the reactions of the radicals (•OH and •NO2) derived from peroxynitrous acid with phenol have been studied using density functional theory (DFT) at the B3LYP/6-311++G(d, p)//B3LYP/6-311G(d, p) level. The geometries of all the molecules were optimized, and the harmonic vibration frequencies and the energies were calculated as well. The calculation results show that the primary products of the reaction of peroxynitrous acid and phenol are o-hydroxyphenol and p-hydroxyphenol, due to their relatively lower activation barriers. The conclusion is in good agreement with the corresponding experimental data. In addition, the effects of solvents on these reactions were also investigated. The results suggest that polar solvents can reduce the activation energy and hence facillate the occurrence of reactions.

Key words: Peroxynitrous acid, Radical, Phenol, Density functional theory