Theoretical Investigation for Two-state Reactivity of CO2 Hydrogenation Catalyzed by Ru in Gas Phase

摘要

Gas-phase CO_2 catalyzed activation hydrogenation by Ru atoms was studied with density functional theory. Based on the structure optimization of different potential energy surfaces,there are two crossing points between singlet and triplet potential energy surfaces and there is a crossing point between quintet and triplet potential energy surfaces in the whole catalytic cycle. Spin transition probabilities in the vicinity of the intersections have been calculated by the Landau-Zener model theory. There are three minimum energy crossing points(MECPs) with strong spin-orbital coupling effect and higher spin transition probability,and all spin inversion occurred in s orbital and different d orbitals of ruthenium,indicating this is a typical two-state reactivity(TSR) reaction. Finally,the lowest energy reaction path is ensured.