A Spectroscopic and Computational Study of Cm3+ Incorporation in Lanthanide Phosphate Rhabdophane (LnPO4·0.67H2O) and Monazite (LnPO4)

This study investigates the incorporation of the minor actinide curium (Cm3+) in a series of synthetic La1–xGdxPO4 (x = 0, 0.24, 0.54, 0.83, 1) monazite and rhabdophane solid-solutions. To obtain information on the incorporation process on the molecular scale and to understand the distribution of the dopant in the synthetic phosphate phases, combined time-resolved laser fluorescence spectroscopy and X-ray absorption fine structure spectroscopy investigations were conducted and complemented with ab initio atomistic simulations. We found that Cm3+ is incorporated in the monazite endmembers (LaPO4 and GdPO4) on one specific, highly ordered lattice site. The intermediate solid-solutions, however, display increasing disorder around the Cm3+ dopant as a result of random variations in nearest neighbor distances. In hydrated rhabdophane, and especially its La-rich solid-solutions, Cm3+ is preferentially incorporated on nonhydrated lattice sites. This site occupancy is not in agreement with the hydrated rhabdophan...