Oriented external electric fields regulating the oxidation reaction ofCH(4)catalyzed byMn-corrolazine

摘要

Mn-corrolazine-catalyzed CH(4)oxidation, as well as the regulation of its oriented external electric fields (OEEFs), is systematically studied using the first-principle calculations. Extensive density functional calculations show that the activation energy of CH(4)oxidation catalyzed by Mn-corrolazine is up to 38.5 kcal/mol in the field-free condition. However, when the OEEF is applied, the reactant and the transition state of the oxidation reaction are stabilized, originating from an attractive interaction between the increased dipole moment and the applied fields. Furthermore, when the field is negative, the activation energy decreases as the field increases. Especially for the negative field along the intrinsic Mn-O reaction axis perpendicular to the corrolazine ring, of which the orientation is easily aligned in practical applications, when its intensity reaches -0.015 a.u., the activation energy of CH(4)oxidation is reduced to 25.0 kcal/mol.