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Abstract: The entire reaction mechanism for the gas phase CO–CO2 conversion by FeO+ is discussed by means of the density functional theory and the intrinsic reaction coordinate approach. The calculated results have strongly indicated that the reaction of is a spin-forbidden reaction between the quartet and the sextet potential energy surfaces (PESs). There is a crossing point between the quartet and the sextet potential energy surfaces which may play a significant role in this reaction, by which the activation energy can be decreased from −15.1 to −56.4kJmol−1 at the reaction system. [Copyright &y& Elsevier]

Abstract: The reaction of La+ with CH3F, which was selected as a representative system of the activation of C–F bond in fluorohydrocarbons by bare lanthanide cations, has been examined using density functional theory (DFT) to explore more integrated reaction pathways and mechanisms on both singlet and triplet potential energy surfaces (PESs). A direct fluorine abstraction mechanism and an insertion–elimination mechanism were revealed, the related thermochemistry data involved in reaction of La++CH3F were determined. The crossing points (CPs) have been found by means of single-point computations as a function of the structural change along the intrinsic reaction coordinate (IRC) in this manuscript. The present results not only support the existing reaction conclusions inferred from early experimental data, but also complement the pathway and mechanism for this reaction, which can act as a guide for further experimental researches and theoretical investigations. [Copyright &y& Elsevier]