Accurate determination of reaction energetics and kinetics of the HO2˙ + O3 → OH˙ + 2O2 reaction

Abstract

In the present work, we have studied the HO₂˙ + O₃ → HO˙ + 2O₂ reaction using chemical kinetics and quantum chemical calculations. We have employed the post-CCSD(T) method to estimate the barrier height and reaction energy for the title reaction. In the post-CCSD(T) method, we have included zero point energy corrections, contributions from full triple excitations and partial quadratic excitations at the coupled-cluster level, and core corrections. We have also computed the reaction rate in the temperature range of 197–450 K and found good agreement with all the available experimental results. In addition, we have also fitted the computed rate constants with the Arrhenius expression and obtained an activation energy of 1.0 ± 0.1 kcal mol⁻¹, almost identical to the value recommended by IUPAC and JPL.