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Etude par la Théorie de la Fonctionnelle de la Densité des propriétés électroniques et magnétiques de complexes de fer. Application aux systèmes de types Catalase et Fer-Soufre

Maylis Orio 1
1 RM [?-2019] - Magnetic Resonance [?-2019]
MEM - Modélisation et Exploration des Matériaux : DRF/IRIG/MEM
Abstract : This PhD work is divided into two parts and aims at modeling some spectroscopic quantities (Mössbauer, EPR and magnetism) measured in iron containing bioinorganic systems with Density Functional Theory (DFT). The first part of this work deals with the theoretical calculation of two Mössbauer parameters: the isomeric shift Δ and the quadrupole splitting ΔEQ. First, correlations between calculations and experimental data have been established for simple iron complexes. Second, we have been interested in the investigation of a biological system, catalase, an iron containing heme, and we have tried to characterize its various forms. The second part of this work was devoted to rationalizing the variations of two parameters: the EPR g-average value, gav (= (∑gi)/3), and the effective exchange coupling constant Jeff. We have considered a set of [2Fe-2S] clusters in biological systems (ferredoxins, Rieske proteins, xanthine oxydases, etc). We have modeled these quantities with a phenomenological model involving the competition between two antagonist terms: the double exchange term B which reflects electronic delocalization between the iron sites and the trapping term ΔE which preferentially localizes the reducing electron on one iron site. We have been able to express analytically gav et Jeff as a function of the ratio ΔE/B allowing us to explain the source of the observed variations.
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https://tel.archives-ouvertes.fr/tel-00178652
Contributor : Maylis Orio <>
Submitted on : Thursday, October 11, 2007 - 6:13:40 PM
Last modification on : Monday, July 20, 2020 - 2:04:02 PM
Long-term archiving on: : Friday, November 25, 2016 - 6:24:27 PM

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Maylis Orio. Etude par la Théorie de la Fonctionnelle de la Densité des propriétés électroniques et magnétiques de complexes de fer. Application aux systèmes de types Catalase et Fer-Soufre. Autre. Université Joseph-Fourier - Grenoble I, 2007. Français. ⟨tel-00178652⟩

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