Theoretical Elucidation of Am(III)/Cm(III) Separation Mechanism with Diamide-type Ligands Using Relativistic Density Functional Theory Calculation

We elucidated the separation mechanism between Am­(III) and Cm­(III) ions by using two different types of diamide ligands, diglycolamide (DGA) and alkylated diamide amine (ADAAM), by means of the density functional theory technique and electron density analysis. The molecular geometries and formation reactions of the metal–ligand complexes were modeled by using [M­(DGA)3]3+ and [M­(ADAAM)­(NO3)3(H2O)]. We successfully reproduced Cm­(III) selectivity over Am­(III) with DGA and Am­(III) selectivity over Cm­(III) with ADAAM. Furthermore, we analyzed the bonding properties between the metal ion and the diamide-type ligands by using model complexes, [M­(DGA)3]3+ and [M­(ADAAM)­(NO3)3(H2O)], and revealed the differences in terms of the bond dissociation energy and the metal 5f orbital participation in the covalency between the Am­(III) and the Cm­(III) complexes. It was suggested that the differences were key factors to understand the Am­(III)/Cm­(III) selectivity.