# The MgCO$_3$-CaCO$_3$-Li$_2$CO$_3$-Na$_2$CO$_3$-K$_2$CO$_3$ Carbonate Melts: Thermodynamics and Transport Properties by Atomistic Simulations

## TL;DR

This study uses atomistic simulations to investigate the thermodynamics and transport properties of complex carbonate melts relevant to Earth's mantle, extending force fields to include Mg and Ca components and validating against experimental data.

## Contribution

The paper introduces a new force field for Mg- and Ca-bearing carbonate melts and demonstrates its accuracy in modeling their thermodynamic and transport properties across wide temperature and pressure ranges.

## Key findings

- Force field accurately models MgCO3 and CaCO3 melts.
- Simulation results agree well with experimental data.
- First study to explore transport properties of magnesite and dolomite melts.

## Abstract

Atomistic simulations provide a meaningful way to determine the physico-chemical properties of liquids in a consistent theoretical framework. This approach takes on particular usefulness for the study of molten carbonates, in a context where thermodynamic and transport data are crucially needed over a large domain of temperatures and pressures (to ascertain the role of these melts in geochemical processes) but are very scarce in the literature, especially for the calco-magnesian compositions prevailing in the Earth's mantle. Following our work on Li2CO3-Na2CO3-K2CO3 melts, we extend our force field to incorporate Ca and Mg components. The empirical interaction potentials are benchmarked on the density data available in the experimental literature (for the crystals and the K2Ca(CO3)2 melt) and on the liquid structure issued from ab initio molecular dynamics simulations. Molecular dynamics simulations are then performed to study the thermodynamics, the microscopic structure, the diffusion coefficients, the electrical conductivity and the viscosity of molten Ca, Mg-bearing carbonates up to 2073 K and 15 GPa. Additionally, the equation of state of a Na-Ca-K mixture representative of the lavas emitted at Ol Doinyo Lengai (Tanzania) is evaluated. The overall agreement between the MD results and the existing experimental data is very satisfying and provides evidence for the ability of the force field to accurately model any MgCO3-CaCO3-Li2CO3-Na2CO3-K2CO3 melt over a large T - P range. Moreover it is the first report of a force field allowing to study the transport properties of molten magnesite (MgCO3) and molten dolomite (CaMg(CO3)2).