Oxidation State Localized Orbitals: A Method for Assigning Oxidation States Using Optimally Fragment-Localized Orbitals and a Fragment Orbital Localization Index

• Published in: Journal of chemical theory and computation 2022-01, Vol.18 (1), p.309-322
• Main Authors: Gimferrer, Martí, Aldossary, Abdulrahman, Salvador, Pedro, Head-Gordon, Martin
• Format: Article
• Language: English
• Subjects: Algorithms; Chemical bonds; Chemical reactions; Coordination compounds; Density functional theory; Localization; Mathematical analysis; Metal oxides; Orbitals; Oxidation; Quantum Electronic Structure; Redox reactions; Transition metal compounds; Valence
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.1c01011

Oxidation states represent the ionic distribution of charge in a molecule and are significant in tracking redox reactions and understanding chemical bonding. While effective algorithms already exist based on formal Lewis structures as well as using localized orbitals, they exhibit differences in challenging cases where effects such as redox noninnocence are at play. Given a density functional theory (DFT) calculation with chosen total charge and spin multiplicity, this work reports a new approach to obtaining fragment-localized orbitals that is termed oxidation state localized orbitals (OSLO), together with an algorithm for assigning the oxidation state using the OSLOs and an associated fragment orbital localization index (FOLI). Evaluating the FOLI requires fragment populations, and for this purpose a new version of the intrinsic atomic orbital (IAO) scheme is introduced in which the IAOs are evaluated using a reference minimal basis formed from on-the-fly superposition of atomic density (IAO-AutoSAD) calculations in the target basis set and at the target level of theory. The OSLO algorithm is applied to a range of challenging cases including high valent metal oxide complexes, redox noninnocent NO and dithiolate transition metal complexes, a range of carbene-containing TM complexes, and other examples including the potentially inverted ligand field in [Cu­(CF3)4]−. Across this range of cases, OSLO produces generally satisfactory results. Furthermore, in borderline cases, the OSLOs and associated FOLI values provide direct evidence of the emergence of covalent interactions between fragments that nicely complements existing approaches.