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Open AccessArticle

Can We Safely Obtain Formal Oxidation States from Centroids of Localized Orbitals?

Departament de Química and Institut de Química Computacional i Catàlisi, Universitat de Girona, Maria Aurèlia Capmany 69, 17003 Girona, Spain
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Academic Editors: Diego Andrada and Israel Fernández
Molecules 2020, 25(1), 234; https://doi.org/10.3390/molecules25010234
Received: 5 December 2019 / Revised: 29 December 2019 / Accepted: 2 January 2020 / Published: 6 January 2020
(This article belongs to the Special Issue Modern Computational Methods for Chemical Bonding and Reactivity)
The use of centroids of localized orbitals as a method to derive oxidation states (OS) from first-principles is critically analyzed. We explore the performance of the closest-atom distance criterion to assign electrons for a number of challenging systems, including high-valent transition metal compounds, π-adducts, and transition metal (TM) carbenes. Here, we also introduce a mixed approach that combines the position of the centroids with Bader’s atomic basins as an alternative criterion for electron assignment. The closest-atom criterion performs reasonably well for the challenging systems, but wrongly considers O-H and N-H bonds as hydrides. The new criterion fixes this problem, but underperforms in the case of TM carbenes. Moreover, the OS assignment in dubious cases exhibit undesirable dependence on the particular choice for orbital localization. View Full-Text
Keywords: oxidation states; localized orbitals; metal carbenes; wavefunction analysis oxidation states; localized orbitals; metal carbenes; wavefunction analysis
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MDPI and ACS Style

Gimferrer, M.; Comas-Vilà, G.; Salvador, P. Can We Safely Obtain Formal Oxidation States from Centroids of Localized Orbitals? Molecules 2020, 25, 234. https://doi.org/10.3390/molecules25010234

AMA Style

Gimferrer M, Comas-Vilà G, Salvador P. Can We Safely Obtain Formal Oxidation States from Centroids of Localized Orbitals? Molecules. 2020; 25(1):234. https://doi.org/10.3390/molecules25010234

Chicago/Turabian Style

Gimferrer, Martí; Comas-Vilà, Gerard; Salvador, Pedro. 2020. "Can We Safely Obtain Formal Oxidation States from Centroids of Localized Orbitals?" Molecules 25, no. 1: 234. https://doi.org/10.3390/molecules25010234

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