Reaction path hamiltonian study of the isomerization of the methoxy radical

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The reaction path hamiltonian of Miller, Handy and Adams was used to investigate the isomerization CH3O → CH2OH, which is of interest in atmospheric chemistry. The equilibrium configurations, transition state and reaction path were calculated using the restricted Hartree-Fock (RHF) and complete active space self consistent field (CASSCF) methods, with STO-3G and double zeta basis sets. The microcanonical and temperature dependent rate constants were calculated with and without tunnelling using RHF and CASSCF with an STO-3G basis. It was found that the tunnelling correction is important, but that at temperatures below 1000 K the reaction does not proceed significantly.