Atomistic simulations of molten carbonates: Thermodynamic and transport properties of the LiCO-NaCO-KCO system.

Although molten carbonates only represent, at most, a very minor phase in the Earth's mantle, they are thought to be implied in anomalous high-conductivity zones in its upper part (70-350 km). Besides, the high electrical conductivity of these molten salts is also exploitable in fuel cells. Here, we report quantitative calculations of their properties, over a large range of thermodynamic conditions and chemical compositions, which are a requisite to develop technological devices and to provide a better understanding of a number of geochemical processes. To model molten carbonates by atomistic simulations, we have developed an optimized classical force field based on experimental data of the literature and on the liquid structure issued from ab initio molecular dynamics simulations performed by ourselves. In implementing this force field into a molecular dynamics simulation code, we have evaluated the thermodynamics (equation of state and surface tension), the microscopic liquid structure and the transport properties (diffusion coefficients, electrical conductivity, and viscosity) of molten alkali carbonates (LiCO, NaCO, KCO, and some of their binary and ternary mixtures) from the melting point up to the thermodynamic conditions prevailing in the Earth's upper mantle (∼1100-2100 K, 0-15 GPa). Our results are in very good agreement with the data available in the literature. To our knowledge, a reliable molecular model for molten alkali carbonates covering such a large domain of thermodynamic conditions, chemical compositions, and physicochemical properties has never been published yet.