Quantum mechanical DFT elucidation of CO2catalytic conversion mechanisms: Three examples

Computational modeling has a key role in the field of catalysis. Involved intermediates, as reactions should be fast, are difficult to intercept and computational investigations represent a good tool for the elucidation of reaction mechanisms, whose knowledge can be indispensable for the optimization of existing catalysts and the design of new ones. In this perspective, three illustrative examples, from our recent work in the field of homogeneous and enzymatic catalysis, of catalytic processes addressed to convert carbon dioxide into high added value compounds are discussed. For all three systems, quantum mechanical density functional theory calculations have been carried out to describe the corresponding potential energy surfaces, although different computational procedures have been used according to the size of the studied systems. The reported outcomes show as quantum chemical methodologies allow to examine different mechanistic proposals, at structural and energetic levels, discarding unviable mechanistic alternatives, and proposing pathways consistent with available experimental data.