Relativistic density functional investigation of Pu(H2O)n3+ clusters

Abstract

The solvation of the Pu{sup 3+} ion in water was investigated using relativistic density functional theory including generalized gradient corrections. Binding energies and optimized geometries for different coordination numbers of water molecules [Pu(H{sub 2}O){sub n}{sup 3+}, n=6, 8, 9, 10, 12] around the ion were calculated. The results indicate that the first solvation shell of Pu{sup 3+} is likely to contain eight or possibly nine waters with a Pu-O bond length of 2.51-2.55 {angstrom}. The theoretical results are compared with two recent EXAFS experiments on the Pu{sup 3+} aqueous system.