Metal complexation and ion hydration in low density hydrothermal fluids: Ab initio molecular dynamics simulation of Cu(I) and Au(I) in chloride solutions (25-1000 °C, 1-5000 bar)

Low-density supercritical fluids are suspected of being able to transport metals, but it is unclear what the speciation/complexation would be in such conditions. In this work, we used ab initio molecular dynamics simulations to investigate the complexation, ion association and hydration of Cu+ and Au+ in NaCl brines as a function of solution density, from ambient to supercritical conditions (to 1000 °C, 5000 bar). Cu(I) and Au(I) form distorted linear complexes with two chloride ligands (i.e., CuCl2− and AuCl2−) in subcritical chloride brines. We have discovered that these charged complexes remain in high density supercritical fluids even at high temperature; however, with decreasing density, these complexes become progressively neutralized by ion association with Na+ to form low-charge (NanCuCl2)n−1 and (NanAuCl2)n−1 complexes. In these species, the Na+ ion is very weakly bonded in the outer coordination sphere, resulting in highly disordered structures and fast (few picoseconds) exchange among coordinated and solvent Na+ ions. Thermodynamic models to predict the solubility of metals in low-density magmatic or metamorphic fluids must account for these species. In addition, we found that the number of water molecules (i.e., the hydration number) surrounding the Cu+, Au+, Na+ and Cl− ions decreases linearly when fluid density decreases; this supports empirical thermodynamic models that correlate the stability constants of complexation reactions with solvent density. The traditional Born-model description explains the ion association as resulting from the decreased dielectric constant of the solvent. However at a molecular level, the increased ion association results from the increase in translational entropy associated with ion dehydration.