DFT Study for the Reduction of N2O(1Σ+) with CO(1Σ+) Catalyzed by Cr+

Abstract

AbstractThe mechanism of the reaction N2O(1Σ+)+CO(1Σ+)→N2(1Σ)+CO2(1Σ) catalyzed by Cr+ has been investigated on sextet and quartet potential energy surfaces. The reactions are studied by using the UB3LYP density functional method and the standard 6‐311+G(2d) basis sets. The geometries for reactants, the transition states and the products are completely optimized. The result shows that the reaction proceeds in a two‐step manner, each mechanism are insertion‐elimination and rearrangement mechanism. The involved crossing between the two potential energy surfaces have been discussed by means of the intrinsic reaction coordinate (IRC) approach, and the crossing points (CPs) are located. The minimum energy crossing point (MECP) that we obtained by the mathematical algorithm proposed by Harvey et al. has been also employed. Then the action of frontier molecular orbitals in MECPs were illuminated briefly. Finally, O‐atom affinities (OA) testified that the argumentation is thermodynamically allowed.