Quantum chemical study of inner-sphere complexes of trivalent lanthanide and actinide ions on the corundum (0001) surface
-
Robert Polly
Abstract
Sorption of trivalent metal ions onto mineral surfaces is of special relevance in the safety assessment of nuclear waste disposal. In the present quantum chemical study we mainly focused on understanding the interaction of trivalent metal ions (La3+, Eu3+ and Cm3+) with the corundum (0001) the surface. We studied how the structure of the inner-sphere complex at the corundum (0001) surface depends on the deprotonation of the surface and give a prediction for the most likely structure of the inner-sphere complex (bi-, tri- or tetradentate). We approached this question using a cluster model for the surface. By deprotonating the cluster we mimicked a chemical environment at pH values above the point of zero charge. In a first step, we tested the accuracy of Density Functional Theory calculations with the BP86 functional and various basis sets by comparing them with Møller-Plesset perturbation theory of second order on a small chemically similar test system. This is followed by a series of calculations on a large and realistic cluster which is an extended model for the formation of the inner-sphere complex at the corundum (0001) surface. Our calculations predict the highest stability for a species with six water molecules remaining in the first coordination sphere of the metal ions and forming an inner-sphere surface complex attached to three surface oxygen atoms. The formation of the inner-sphere complexes is even more favoured when the coordination takes place via one or two deprotonated surface oxygen atoms.
© by Oldenbourg Wissenschaftsverlag, Karlsruhe, Germany
Articles in the same Issue
- Preface
- Solubility of tetravalent actinides in alkaline CaCl2 solutions and formation of Ca4[An(OH)8]4+ complexes: A study of Np(IV) and Pu(IV) under reducing conditions and the systematic trend in the An(IV) series
- Solubility of triuranyl diphosphate tetrahydrate (TDT) and Na autunite at 23 and 50 °C
- Effect of reduction on the stability of Pu(VI) hydrolysis species
- Retention and redox behaviour of uranium(VI) by siderite (FeCO3)
- Neptunium(V) complexation by natural pyoverdins and related model compounds
- Complexation of Nd(III) with tetraborate ion and its effect on actinide(III) solubility in WIPP brine
- Complexation of Tc(IV) with acetate at varying ionic strengths
- Uranyl photochemistry: decarboxylation of gluconic acid
- Influence of Boom Clay organic matter on the adsorption of Eu3+ by illite – geochemical modelling using the component additivity approach
- The role of green rust in the migration of radionuclides: An overview of processes that can control mobility of radioactive elements in the environment using as examples Np, Se and Cr
- A comparative batch sorption and time-resolved laser fluorescence spectroscopy study on the sorption of Eu(III) and Cm(III) on synthetic and natural kaolinite
- U(VI) sorption on granite: prediction and experiments
- Quantum chemical study of inner-sphere complexes of trivalent lanthanide and actinide ions on the corundum (0001) surface
- Quantum chemical modeling of uranyl adsorption on mineral surfaces
- Interaction of PuO2 thin films with water
- Molecular interactions of plutonium(VI) with synthetic manganese-substituted goethite
- Chlorine speciation in nuclear graphite: consequences on temperature release and on leaching
- Chemical status of U(VI) in cemented waste forms under saline conditions
- Influence of iron redox transformations on plutonium sorption to sediments
- Modelling of a large-scale in-situ migration experiment with 14C-labelled natural organic matter in Boom Clay
- Sorption and diffusion of Eu in sedimentary rock in the presence of humic substance
- Diffusion and sorption of neptunium(V) in compacted montmorillonite: effects of carbonate and salinity
- Uranium(VI) diffusion in low-permeability subsurface materials
- Distribution of Cs and Am in the solution-bentonite colloids-granite ternary system: effect of addition order and sorption reversibility
- Mechanisms of plutonium sorption to mineral oxide surfaces: new insights with implications for colloid-enhanced migration
- Understanding uranium behaviour at the Askola uranium mineralization
Articles in the same Issue
- Preface
- Solubility of tetravalent actinides in alkaline CaCl2 solutions and formation of Ca4[An(OH)8]4+ complexes: A study of Np(IV) and Pu(IV) under reducing conditions and the systematic trend in the An(IV) series
- Solubility of triuranyl diphosphate tetrahydrate (TDT) and Na autunite at 23 and 50 °C
- Effect of reduction on the stability of Pu(VI) hydrolysis species
- Retention and redox behaviour of uranium(VI) by siderite (FeCO3)
- Neptunium(V) complexation by natural pyoverdins and related model compounds
- Complexation of Nd(III) with tetraborate ion and its effect on actinide(III) solubility in WIPP brine
- Complexation of Tc(IV) with acetate at varying ionic strengths
- Uranyl photochemistry: decarboxylation of gluconic acid
- Influence of Boom Clay organic matter on the adsorption of Eu3+ by illite – geochemical modelling using the component additivity approach
- The role of green rust in the migration of radionuclides: An overview of processes that can control mobility of radioactive elements in the environment using as examples Np, Se and Cr
- A comparative batch sorption and time-resolved laser fluorescence spectroscopy study on the sorption of Eu(III) and Cm(III) on synthetic and natural kaolinite
- U(VI) sorption on granite: prediction and experiments
- Quantum chemical study of inner-sphere complexes of trivalent lanthanide and actinide ions on the corundum (0001) surface
- Quantum chemical modeling of uranyl adsorption on mineral surfaces
- Interaction of PuO2 thin films with water
- Molecular interactions of plutonium(VI) with synthetic manganese-substituted goethite
- Chlorine speciation in nuclear graphite: consequences on temperature release and on leaching
- Chemical status of U(VI) in cemented waste forms under saline conditions
- Influence of iron redox transformations on plutonium sorption to sediments
- Modelling of a large-scale in-situ migration experiment with 14C-labelled natural organic matter in Boom Clay
- Sorption and diffusion of Eu in sedimentary rock in the presence of humic substance
- Diffusion and sorption of neptunium(V) in compacted montmorillonite: effects of carbonate and salinity
- Uranium(VI) diffusion in low-permeability subsurface materials
- Distribution of Cs and Am in the solution-bentonite colloids-granite ternary system: effect of addition order and sorption reversibility
- Mechanisms of plutonium sorption to mineral oxide surfaces: new insights with implications for colloid-enhanced migration
- Understanding uranium behaviour at the Askola uranium mineralization
