Insights into Uranyl Chemistry from Molecular Dynamics Simulations

First-principles and purely classical molecular dynamics (MD) simulations for complexes of the uranyl ion (UO22+) are reviewed. Validation of CarParrinello MD simulations for small uranyl complexes in aqueous solution is discussed. Special attention is called to the mechanism of ligand-exchange reactions at the uranyl centre and to effects of solvation and hydration on coordination and structural properties. Large-scale classical MD simulations are surveyed in the context of liquidliquid extraction, with uranyl complexes ranging from simple hydrates to calixarenes, and nonaqueous phases from simple organic solvents and supercritical CO2 to ionic liquids.