Computational investigation of thermochemistry and kinetics of the reaction between n-butyl peroxy and hydroperoxyl radicals

Abstract

The energetics, thermochemistry and kinetics for the reaction between n-butyl peroxy radical and HO2 radical was computed using CCSD(T)/aug-cc-pVDZ// B3LYP/6-311G(d,p) level of theory coupled with Canonical Variational Transition state theory incorporating small curvature tunnelling corrections. The H abstraction pathway involving addition–elimination mechanism on the triplet energy surface was found to be most feasible reaction pathway. The calculated rate coefficients showed a negative temperature dependency in the studied range of 200 to 400 K. The Arrhenius expression for the title reaction was derived as, ktotal = 1.35 × 10−16 exp(3703/T) cm3molecule−1 s−1.