Titre : | Complexes de Lanthanides et d’Actinides trivalent à ligands fonctionnels polydentates. Effet du substituant et du contre-ion sur la différentiation Ln (III)/An (III) |
Auteurs : | Sihem Aggoun, Auteur ; Lotfi Belkhiri, Directeur de thèse |
Type de document : | Thése doctorat |
Editeur : | Biskra [Algérie] : Faculté des Sciences Exactes et des Sciences de la Nature et de la Vie, Université Mohamed Khider, 2010 |
Format : | 1 vol. (91 p.) / 29 cm |
Langues: | Français |
Langues originales: | Français |
Résumé : |
This work aims a relativistic DFT (Density Functional Theory) study of structural and electronic properties of lanthanides and actinides trivalent organometallic complexes in the framework of the Ln(III)/An(III) differentiation. The actinide and lanthanide elements have a similar ionic radius, and then the nuclear wastes management, is confronted to their problematic separation. On the technical level, we used a code ADF2007.01 (Amsterdam Density Functional) and relativistic ZORA/TZP basis coupled with the BP86 and PBE exchange and correlation functionals, whose performance in the theoretical study of heavy elements organometallic systems is well established. The techniques of molecular graphics will be carried out with the help of the software Molekel4.3 and ADF view. The results obtained in this manuscript, have shown that f-elements form essentially ionic bonding with hard donor like RO– and halogens X- However, when the atoms donors are less hard or soft donors, like nitrogen atom, a covalent contribution is obtained with uranium complexes. ı donor and ʌ acceptor ligands as polyazine ligands, shown that in the uranium(III) species, an important covalent character is revealed. While, in the lanthanide Ln(III) cases, the metal-ligand bonding are essentially ionic. This could be drive the selective separation of actinide over lanthanide complexes with ligand as terpyridine or BTP Lewis basis. These results are agree with precedent study of Adamo and co-workers and bring the light on importance of DFT calculation in simulation and modelling of such heavy f-elements compounds associated with ligands mono and poly-azotes like pyridine, pyrazine, bipyridine , terpyridine and BTP, this latter showed a great extractive and selective capacity in the Ln (III)/An (III) differentiation. |
Sommaire : |
Introduction générale CHAPITRE 1: -A- Théorie et méthodologie -B--B- Introduction à la chimie des éléments f de Lanthanides (4f) et d’Actinides (5f). CHAPITRE2:Etude des complexes [M(L) 3]+3 et X3M-(L) 3 Effet de la base de Lewis L = Pyridine et Pyrazine et du contre ion (X = F- et Cl-) sur la différentiation Ln(III)/An(III) CONCLUSIONS |
Type de document : | Thése doctorat |
En ligne : | http://thesis.univ-biskra.dz/2481/1/M%C3%A9moire_2010.pdf |
Disponibilité (1)
Cote | Support | Localisation | Statut |
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TCH/09 | Mémoire de magister | bibliothèque sciences exactes | Consultable |