Inorganic Chemistry, Vol.41, No.5, 1315-1319, 2002
Coordination of the neptunyl ion with carbonate ions and water: A theoretical study
The results of a study on the ground-state of monocarbonate, bicarbonate, and tricarbonate complexes of neptunyl using multiconfigurational second-order perturbation theory (CASSCF/CASPT2) are presented. The equilibrium geometries of the complexes corresponding to neptunium in the formal oxidation state (V) have been fully optimized at the CASPT2 level of theory in the presence of an aqueous environment modeled by a reaction field Hamiltonian with a spherical cavity. Some water molecules have been explicitly included in the calculation. This study is consistent with the hypothesis that the monocarbonate complex has a pentacoordinated structure with three water molecules in the first coordination shell and that the bicarbonate complex has a hexacoordinated structure, with two water molecules in the first coordination shell. The typical bond distances are in good agreement with experimental results. The tricarbonate complex was studied with explicit counterions, which resulted in somewhat longer Np-carbonate bond distances than experiment indicates.