Extracting the Americyl Hydration from an Americium Cationic Mixture in Solution: A Combined X-ray Absorption Spectroscopy and Molecular Dynamics Study.

Am(VI) solution chemistry differs from that of lighter actinoids, as U, Pu, and Np, where the actinyl [AnO] is the most stable form and plays an important role in nuclear fuel technology. The behavior of americium in solution shows the trend to stabilize lower oxidation states, mainly Am(III). Riddle and co-workers recently reported the EXAFS and first XANES spectra of an americium-containing aqueous solution where the americyl species is detected in a mixture. We have developed Am-HO and [AmO]-HO intermolecular potentials based on quantum-mechanical calculations to carry out classical MD simulations of these two cations in water. Structural information extracted from the statistical trajectories has been used to simulate EXAFS and XANES spectra of both solutions. For the Am case the theoretical-experimental agreement for both EXAFS and XANES spectra is satisfactory. This is not the case for the [AmO] aqueous solutions. However, when an aqueous solution mixture of both cationic forms in a 55/45 [AmO]/Am ratio is considered, the theoretical-experimental agreement is recovered. EXAFS and XANES spectra which would correspond to a pure [AmO] aqueous solution are proposed. In the XANES case, the main features characterizing the simulated spectrum are consistent with those previously found in the experimental XANES spectra of stable [UO] and [PuO] in water.