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

ABSTRACT: 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

SUBMITTER: Gimferrer M 

PROVIDER: S-EPMC6983110 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature