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Fractionnement isotopique du zinc à l'équilibre par calcul ab initio

Abstract : Isotopic compositions are used to study the biogeochemical cycle of Zn, which is greatly impacted by anthropic activities. However, the interpretation of the measurements performed on natural or synthetic samples requires the knowledge of Zn isotope properties in equilibrium conditions (as reference) and the understanding of the mechanisms that are at the origin of the isotopic composition variations. In this work, we determined by performing quantum calculations, equilibrium Zn isotope fractionation constants in various phases including solids and liquids. We highlighted the crystal-chemical parameters controlling the isotopic properties : Zn interatomic force constant, Zn-first neighbours bond lengths and the electronic charge on atoms involved in the bonding. We carried out a methodological development in order to calculate isotopic properties in liquid phases from molecular dynamics trajectories at a reduced computational cost. We showed through the modelling of aqueous Zn that a reasonable description of van der Waals forces using a non-local exchange correlation functional is required to stabilise the experimentally observed hexaaquo zinc complex over other complexes at room temperature. This work provides a consistent database of equilibrium Zn isotope fractionation constants for experimental works.
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  • HAL Id : tel-01724138, version 1

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Manoj Ducher. Fractionnement isotopique du zinc à l'équilibre par calcul ab initio. Chimie-Physique [physics.chem-ph]. Université Pierre et Marie Curie - Paris VI, 2017. Français. ⟨NNT : 2017PA066318⟩. ⟨tel-01724138⟩

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