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Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers

[Image: see text] The electronic structure of multinuclear transition metal complexes is a highly challenging problem for quantum chemical methods. The problems to be solved for a successful analysis include the following: (1) many unpaired electrons leading to “highly entangled” wave functions that...

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Autores principales: Chilkuri, Vijay Gopal, DeBeer, Serena, Neese, Frank
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6978809/
https://www.ncbi.nlm.nih.gov/pubmed/31247844
http://dx.doi.org/10.1021/acs.inorgchem.9b00974
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author Chilkuri, Vijay Gopal
DeBeer, Serena
Neese, Frank
author_facet Chilkuri, Vijay Gopal
DeBeer, Serena
Neese, Frank
author_sort Chilkuri, Vijay Gopal
collection PubMed
description [Image: see text] The electronic structure of multinuclear transition metal complexes is a highly challenging problem for quantum chemical methods. The problems to be solved for a successful analysis include the following: (1) many unpaired electrons leading to “highly entangled” wave functions that cannot be calculated by standard electronic structure methods, (2) drastic differences between the one-particle and many-particle spectra and a high density of low-lying states, and (3) the interpretation of such highly complex wave functions in chemical terms. In this work, we continue our research on oligonuclear clusters by presenting an in-depth analysis of the electronic structure of a prototypical iron–sulfur (Fe(2)S(2)) dimer. Accurate wave functions are obtained from a variety of advanced wave function based methods. The wave function results are interpreted in terms of an effective Hamiltonian that in turn is parametrized in terms of the angular overlap model (AOM) that provides the chemical insights that we are striving for. A hierarchical analysis allows us to interpret the local electronic structure in terms of the thiolate, sulfide ligands, and metal–metal interaction strengths. The many-particle spectrum is analyzed in terms of configurations involving ligand and metal centers. Finally, we are able to derive simple yet effective interpretations of ligand interaction strengths, the metal–metal interaction strength, and the low-lying many-particle spectrum of the Fe(2)S(2) dimer.
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spelling pubmed-69788092020-01-27 Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers Chilkuri, Vijay Gopal DeBeer, Serena Neese, Frank Inorg Chem [Image: see text] The electronic structure of multinuclear transition metal complexes is a highly challenging problem for quantum chemical methods. The problems to be solved for a successful analysis include the following: (1) many unpaired electrons leading to “highly entangled” wave functions that cannot be calculated by standard electronic structure methods, (2) drastic differences between the one-particle and many-particle spectra and a high density of low-lying states, and (3) the interpretation of such highly complex wave functions in chemical terms. In this work, we continue our research on oligonuclear clusters by presenting an in-depth analysis of the electronic structure of a prototypical iron–sulfur (Fe(2)S(2)) dimer. Accurate wave functions are obtained from a variety of advanced wave function based methods. The wave function results are interpreted in terms of an effective Hamiltonian that in turn is parametrized in terms of the angular overlap model (AOM) that provides the chemical insights that we are striving for. A hierarchical analysis allows us to interpret the local electronic structure in terms of the thiolate, sulfide ligands, and metal–metal interaction strengths. The many-particle spectrum is analyzed in terms of configurations involving ligand and metal centers. Finally, we are able to derive simple yet effective interpretations of ligand interaction strengths, the metal–metal interaction strength, and the low-lying many-particle spectrum of the Fe(2)S(2) dimer. American Chemical Society 2019-06-20 2020-01-21 /pmc/articles/PMC6978809/ /pubmed/31247844 http://dx.doi.org/10.1021/acs.inorgchem.9b00974 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Chilkuri, Vijay Gopal
DeBeer, Serena
Neese, Frank
Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers
title Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers
title_full Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers
title_fullStr Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers
title_full_unstemmed Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers
title_short Ligand Field Theory and Angular Overlap Model Based Analysis of the Electronic Structure of Homovalent Iron–Sulfur Dimers
title_sort ligand field theory and angular overlap model based analysis of the electronic structure of homovalent iron–sulfur dimers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6978809/
https://www.ncbi.nlm.nih.gov/pubmed/31247844
http://dx.doi.org/10.1021/acs.inorgchem.9b00974
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