Density Functional Approximations for Consistent Spin and Oxidation States of Oxoiron Complexes

22 July 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

We report here a computational study on a series of FeII, FeIIIand FeIVhydroxo/oxo-iron complexes with a broad palette of ligands. We are interested in assessing the robustness of widely used density functionals for their prediction and description of structures and spin states for the examined oxoiron complexes. We have used a variety of density functional approximations (S12g, LDA, BP86-D3, OPBE, SSB-D, B3LYP-D3, S12h and MVS), in all cases including solvation and relativistic effects explicitly. One of the main observations of this detailed study is the excellent performance of S12g for both accurate structures and spin state splittings. Moreover, our results show that in general all density functionals can be used as a reliable computational tool for reproducing and predicting geometries, determining the oxidation state of iron, and most are able as well to providing good descriptions of spin state energetics.

Keywords

Spin states
Density functional approximations
High-valent transition metals
Iron-oxo complexes
Inorganic Chemistry

Supplementary materials

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Manuscript 20190721
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SuppInfo Tables
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SuppInfo Structures
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SuppInfo ScandiumData
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SuppInfo Full 20190721
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