Density functional theoretical analysis of structure, bonding, interaction and thermodynamic selectivity of hexavalent uranium (UO 2 2+ ) and tetravalent plutonium (Pu 4+ ) ion complexes of tetramethyl diglycolamide (TMDGA)

摘要: In the well-known PUREX process, tertiary butyl phosphate shows preferential extraction of UO2 2+ over Pu4+, whereas tetraoctyl diglycolamide (TODGA) displays reverse selectivity. The reversal selectivity toward has been investigated here theoretically by considering shorter analogue TODGA, tetramethyl (TMDGA). Structure, bonding, energetic parameter and thermodynamic parameters Pu4+ ions with TMDGA in gas solvent phase have reported order to understand their complexation behavior. calculation performed generalized gradient approximated BP86 density functional hybrid B3LYP employing SVP TZVP basis set. calculated structure obtained at BP86/SVP level optimization is found be close agreement experimental data. free energy extraction, ΔG ext, from aqueous dodecane computed using Born-Haber cycle conjunction COSMO (conductor like screening model) solvation approach. predicted exergonic for explicit monomer water model. ion shown higher than that as observed experiment. Further, suitability non-polar solvents organic diluents confirmed decreased increasing dielectric constant solvents. Natural population orbital analysis indicate electrostatic small covalent nature interactions between metal tridentate chelating ligand. results presented might helpful designing new ligands efficient actinides.