Reaction‐path dynamics and theoretical rate constants for the reaction CH4 + O3 → HOOO + CH3

Abstract

AbstractWe present a direct ab initio dynamics study of thermal rate constants of the hydrogen abstraction reaction of CH4 + O3 → HOOO +CH3. The geometries of all the stationary points are optimized at MPW1K/6‐31+G(d,p), MPWB1K/6‐31+G(d,p), and BHandHLYP/6‐31+G(d,p) levels of theory. The energies are refined at a multi‐high‐level method. The extended Arrhenius expression fitted from the CVT/SCT and μVT/Eckart rate constants of ozonolysis of methane in the temperature range 200–2500 K are kCVT/SCT(T) = 5.96 × 10−29T4.49e(−17321.3/T) and kμVT/Eckart(T) = 7.92 × 10−29T4.46e(−17301.7/T), respectively. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007