Molecular modelling of rare earth element complexation in subduction zone fluids

Complexation of (trace) elements in fluids plays a critical role in determining element mobility in subduction zones, but to date, the atomic-scale processes controlling elemental solubilities are poorly understood. As a first step towards computer simulation of element complexation in subduction zone fluids, a thermodynamic cycle was developed to investigate the hydration environment and energetics of lanthanide complexes using density functional theory. The first solvation shell is explicitly defined and the remaining part of the aqueous fluid is modelled using a polarisable continuum model, which allows extrapolation to a broad pressure and temperature range. We illustrate our method by comparing solvation of lanthanide series elements in H