We propose a theoretical approach, based on both quantum analyses (energy decomposition analysis and topological analysis of the chemical bond) and classical molecular dynamics, for the study of f-element complexes. First, we introduce the different QM methods adapted to the study of f-elements and use them for geometry optimization and interaction energy calculations of the model system [M (OH2)]m+ where M is a lanthanide or actinide cation. We then perform energy decomposition analysis to quantify the physical nature of the metal-ligand interaction in terms of the different contributions. Furthermore, the different energy contributions will be used as reference curves for the parameterization of the polarizable force fields AMOEBA and SIBFA. Next, starting from the optimized geometries, we establish the reference diabatic dissociation curves at high level of theory so as to take into account the multi-reference nature of the systems. These dissociation curves will also be used for parameterization of the AMOEBA potential. We then propose a three step validation protocol as well as a first application, it being the computation of Gibbs hydration free energies for the f-element cations. We also propose an extension of the SIBFA force field to trivalent lanthanide ions and tetravalent actinide ions. Last, we use the topological analysis approaches of ELF and NCI to investigate the nature of the different interactions in Gadolinium(III) model and real systems. The aim of the whole study was to develop and apply different theoretical approaches so as to be able to discriminate between lanthanide and actinide cations
Static and dynamic modelling of lanthanide and actinide cations in solution