Geofluids (2010) 10, 41–57
Complexation by ligands in hydrothermal brines is a fundamental step in the transport of metals in the Earth's crust and the formation of ore deposits. Thermodynamic models of mineral solubility require an understanding of metal complexation as a function of pressure, temperature and composition. Over the past 40 years, mineral solubilities and complexation equilibria under hydrothermal conditions have been predicted by extrapolating thermodynamic quantities using equations of state based on the Born model of solvation. However, advances in theoretical algorithms and computational facilities mean that we can now explore hydrothermal fluids at the molecular level. Molecular or atomistic models of hydrothermal fluids avoid the approximations of the Born model and are necessary for any reliable prediction of metal complexation. First principles (quantum mechanical) calculations based on density functional theory can be easily used to predict the structures and relative energies of metal complexes in the ideal gas phase. However, calculations of metal complexation in condensed fluids as a function of temperature and pressure require sampling the configuration degrees of freedom using molecular dynamics (MD). Simulations of dilute solutions require very large systems (thousands of atoms) and very long simulation times; such calculations are only practical by treating the interatomic interactions using classical two- or three-body interatomic potentials. Although such calculations provide some fundamental insights into the nature of crustal fluids, simple two- or three-body classical potentials appear to be inadequate for reliably predicting metal complexation, especially in covalent systems such as Sn2+, Au3+ and Cu+. Ab initio MD (i.e. where the bonding is treated quantum mechanically, but the molecular motions are treated classically) avoids the use of interatomic potentials. These calculations are practical for systems with hundreds of atoms over short times (<10 psec) but enable us to predict complexation as a function of pressure, temperature and composition. In this paper, I provide an introductory outline of the computational methods and illustrations of their application to NaCl brines and the complexation of Cu, Au, Sn and Zn.