Is Change of Spin State Critical for 3d Transition Metal Carbon Monoxide Bonding?
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Transition metal carbonyl (TM-CO) interaction is seen in different areas, including catalysts for CO2 reduction and biological processes involving CO gas. Due to the complex occupation of 3d orbitals, the spin state can change when a TM binds with various gas molecules. In this study, we evaluated the simplest of such spin crossover reactions: 3d TM atom + CO in detail using B3LYP/6-31+G(d,p). Previous studies on TM-CO by Fournier evaluated the dissociation limit and adduct energies and compared spin states. In the present study, we extended the study to include the calculation of the association potential energy curve. We focused on finding the crossing point of two spin states as a function of the TM-C bond length. We also evaluated the relationship between the change of spin state and stable binding between the TM atom and the CO molecule. We found that Sc, Ti, Fe, Co, and Ni + CO are candidates to be spin crossover reactions that change spin upon TM-CO bond formation. Furthermore, among the 3d TM atoms, the most strongly binding TM atoms were Ni, Ti, Fe, and Co, which showed spin state change upon bonding.
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