The oxidation state (OS) concept has been used extensively in the study of transition-metal compounds and their reactions. In particular, this formally-defined concept is used to interpret many experimental results. However, a fundamental theoretical basis for the OS concept through determination by quantum-mechanical calculations has been lacking. In this work, we introduce a novel theoretical approach for determining OS from quantum-mechanical calculations. For a transition-metal ion, for example, the orbital mixing contribution to the charge allocated to the ion is separated from that due to the actual occupation of the d-orbitals from which the OS can then be inferred. Accompanying the method is a simple and unambiguous definition of OS, which contributes to the resolution of the long-standing problem of using OS in quantum mechanical calculations. We report the application of this approach to different transition-metal systems: molecular complexes, ruthenium-dye molecules, ruthenium complexes with non-innocent ligands and bulk semiconductors.Reference:P. H.-L. Sit, R. Car, M. H. Cohen, and A. Selloni, Inorg. Chem. 50  , 10259 (2011).

Simple, unambiguous theoretical approach to oxidation state determination via first-principles calculations

243rd National Meeting (2012)

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