Theoretical Insights into Phenanthroline-Based Ligands toward the Separation of Am(III)/Eu(III)

The bistriazinyl-phenanthroline representative ligand, BTPhen, shows excellent extraction and separation ability for trivalent actinides and lanthanides. Herein, we first designed three phenanthroline-based nitrogen-donor ligands (L¹, L², and L³), and then studied the structural and bonding properties as well as thermodynamic properties of the probable complexes, ML(NO₃)₃ (M = Am or Eu and L = L¹, L², or L³), using scalar relativistic density functional theory. Our charge decomposition analysis revealed an obviously higher charge transfer from the ligand to Am(III) compared with the Eu(III) case for the studied complexes. Spin density analysis further showed a more significant degree of Am-to-ligand spin delocalization and the corresponding spin polarization on the ligands. According to the thermodynamic analysis, ligand L³ has the strongest complexation capacity for both Am(III) and Eu(III) ions, while ligand L¹ has the highest Am(III)/Eu(III) selectivity in binary octanol/water solutions. We expected that this work can provide valuable theoretical support for the design of effective ligands for actinide(III)/lanthanide(III) separation in high level liquid waste.