An extensive methodological theoretical study of the kinetics of the benzylperoxy radical isomerization

► Methodological theoretical study of the kinetics of the benzylperoxy radical isomerization. ► Kinetic parameters are calculated using ab initio molecular orbital methods. ► Rate constants are calculated from 600 to 2000 K and compared to the available literature data. ► The rate constants at 773 K calculated are in very good agreement with the literature counterpart.