A theoretical study of the potential energy surface for the reaction OH+CO→CO2+H

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Abstract
The mechanism of the reaction OH+CO→CO2+H is studied theoretically. The potential energy surface is constructed by using ab initio multiconfiguration (MC) SCF and configuration interaction (CI) calculations. The reaction surface Hamiltonian is derived to estimate the hydrogen tunneling probability. It is found that the first step is the trans addition of OH to CO and the trans–cis isomerization is the subsequent step to lead the hydrogen elimination from the HOCO. The rate constant is calculated by using the RRKM equation and the curved Arrhenius temperature dependence, experimentally observed, is obtained. We have found here that the effects of both the hydrogen tunneling from the HOCO to products and the backreaction from the HOCO to the reactants are essential to obtain this temperature dependence.