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Updated: May 29, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Simple, unambiguous theoretical approach to oxidation state determination via first-principles calculations
Patrick H-L Sit1, Roberto Car, Morrel H Cohen
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA. hsit@princeton.edu
Abstract:
We introduce a novel theoretical approach for determining oxidation states (OS) from quantum-mechanical calculations. For a transition-metal ion, for example, the metal-ligand 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 OS can then be inferred. We report the application of this approach to different transition-metal systems: molecular complexes, ruthenium-dye molecules, ruthenium complexes with noninnocent ligands, and bulk semiconductors. The computations were carried out using density-functional theory with a Hubbard U correction. The oxidation states were determined without ambiguity.
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The process of oxidation in a chemical reaction is observed in any of the three forms:

