Modeling separation of lanthanides heterogeneous ligand binding.

Individual lanthanide elements have physical/electronic/magnetic properties that make each useful for specific applications. Several of the lanthanides cations (Ln) naturally occur together in the same ores. They are notoriously difficult to separate from each other due to their chemical similarity. Predicting the Ln differential binding energies (ΔΔ) or free energies (ΔΔ) at different binding sites, which are key figures of merit for separation applications, will help design of materials with lanthanide selectivity. We apply molecular dynamics (AIMD) simulations and density functional theory (DFT) to calculate ΔΔ for Ln coordinated to ligands in water and embedded in metal-organic frameworks (MOFs), and ΔΔ for Ln bonded to functionalized silica surfaces, thus circumventing the need for the computational costly absolute binding (free) energies Δ and Δ. Perturbative AIMD simulations of water-inundated simulation cells are applied to examine the selectivity of ligands towards adjacent Ln in the periodic table. Static DFT calculations with a full Ln first coordination shell, while less rigorous, show that all ligands examined with net negative charges are more selective towards the heavier lanthanides than a charge-neutral coordination shell made up of water molecules. Amine groups are predicted to be poor ligands for lanthanide-binding. We also address cooperative ion binding, , using different ligands in concert to enhance lanthanide selectivity.