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Chilkuri VG, DeBeer S, Neese F. Revisiting the Electronic Structure of FeS Monomers Using ab Initio Ligand Field Theory and the Angular Overlap Model. Inorg Chem. 2017;56(17):10418-10436doi: 10.1021/acs.inorgchem.7b01371.
Chilkuri, V. G., DeBeer, S., & Neese, F. (2017). Revisiting the Electronic Structure of FeS Monomers Using ab Initio Ligand Field Theory and the Angular Overlap Model. Inorganic chemistry, 56(17), 10418-10436. https://doi.org/10.1021/acs.inorgchem.7b01371
Chilkuri, Vijay Gopal, et al. "Revisiting the Electronic Structure of FeS Monomers Using ab Initio Ligand Field Theory and the Angular Overlap Model." Inorganic chemistry vol. 56,17 (2017): 10418-10436. doi: https://doi.org/10.1021/acs.inorgchem.7b01371
Chilkuri VG, DeBeer S, Neese F. Revisiting the Electronic Structure of FeS Monomers Using ab Initio Ligand Field Theory and the Angular Overlap Model. Inorg Chem. 2017 Sep 05;56(17):10418-10436. doi: 10.1021/acs.inorgchem.7b01371. Epub 2017 Aug 22. PMID: 28829123.
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Inorg Chem. 2017 Sep 05;56(17):10418-10436. doi: 10.1021/acs.inorgchem.7b01371. Epub 2017 Aug 22.

Revisiting the Electronic Structure of FeS Monomers Using ab Initio Ligand Field Theory and the Angular Overlap Model.

Inorganic chemistry

Vijay Gopal Chilkuri, Serena DeBeer, Frank Neese

Affiliations

  1. Max Planck Institute for Chemical Energy Conversion , Stiftstrasse 34-36, D45470 Mülheim an der Ruhr, Germany.

PMID: 28829123 DOI: 10.1021/acs.inorgchem.7b01371

Abstract

Iron-sulfur (FeS) proteins are universally found in nature with actives sites ranging in complexity from simple monomers to multinuclear sites from two up to eight iron atoms. These sites include mononuclear (rubredoxins), dinuclear (ferredoxins and Rieske proteins), trinuclear (e.g., hydrogenases), and tetranuclear (various ferredoxins and high-potential iron-sulfur proteins). The electronic structure of the higher-nuclearity clusters is inherently extremely complex. Hence, it is reasonable to take a bottom-up approach in which clusters of increasing nuclearity are analyzed in terms of the properties of their lower nuclearity constituents. In the present study, the first step is taken by an in-depth analysis of mononuclear FeS systems. Two different FeS molecules with phenylthiolate and methylthiolate as ligands are studied in their oxidized and reduced forms using modern wave function-based ab initio methods. The ab initio electronic spectra and wave function are presented and analyzed in detail. The very intricate electronic structure-geometry relationship in these systems is analyzed using ab initio ligand field theory (AILFT) in conjunction with the angular overlap model (AOM) parametrization scheme. The simple AOM model is used to explain the effect of geometric variations on the electronic structure. Through a comparison of the ab initio computed UV-vis absorption spectra and the available experimental spectra, the low-energy part of the many-particle spectrum is carefully analyzed. We show ab initio calculated magnetic circular dichroism spectra and present a comparison with the experimental spectrum. Finally, AILFT parameters and the ab initio spectra are compared with those obtained experimentally to understand the effect of the increased covalency of the thiolate ligands on the electronic structure of FeS monomers.

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