Structure, reactivity and spectroscopic properties of minerals from lateritic soils:: insights from ab initio calculations

We review here some recent applications of ab initio calculations to the modelling of spectroscopic and energetic properties of minerals, which are key components of lateritic soils or govern their geochemical properties. Quantum mechanical ab initio calculations are based on density functional theory and density functional perturbation theory. Among the minerals investigated, zircon is a typical resistant primary mineral. Its resistance to weathering is at the origin of the peculiar geochemical behaviour of Zr, an element often used in mass balance calculations of continental weathering. Numerical modelling gives a unique picture of the origin of the chemical durability and radiation-induced amorphization of zircon. We also present several applications of ab initio calculations to the description of properties of secondary minerals, such as kaolinite-group minerals and gibbsite. Special attention is given to the calculation of infrared and Raman spectra. Surface properties and particle shape are major properties of finely-divided materials such as clay minerals. We show how theoretical modelling of infrared spectroscopic data provides information on natural samples at both the microscopic (atomic structure) and macroscopic (particle shape) length-scale. The systematic comparison of experimental and theoretical data significantly improves our understanding of mineral transformations during soil formation and evolution in lateritic environments.