TY - JOUR
T1 - Theoretical evaluation of mixed N-, O- donor based TMPhenDA ligand in selective complexation with actinide (III) ions over lanthanide (III) ions
AU - Lipin, Raju
AU - Ebenezer, Cheriyan
AU - Solomon, Rajadurai Vijay
N1 - Publisher Copyright:
© 2021 Elsevier B.V.
PY - 2021/6/15
Y1 - 2021/6/15
N2 - Separation of trivalent actinides An(III) from lanthanide Ln(III) is an extremely challenging task in handling nuclear wastes due to their similar chemical behaviours. Though many designed organic ligands have been used for the separation of Ln(III) from An(III) over the years, selectivity and efficiency is still a matter of concern. This drives us to formulate new efficient ligands, in which mixed –N, –O donor ligands are one of the most emerging and promising agents in separation of An(III) from Ln(III). In this work, recently reported TMPhenDA ligand has been investigated for their complexation behaviour with An(III) (U, Am, Cm) and Ln(III) (Nd, Eu, Gd) ions using scalar relativistic ZORA/DFT calculations. Computed bond parameters show that the An(III) ions bind strongly to the ligand than the lanthanide ions. Bond order and QTAIM analyses have been done on the optimized geometries to understand the bonding situation present in the M3+TMPhenDA complexes. Further, energy decomposition analysis is taken up to assign the percentage covalency of M-N and M-O bonds in these complexes to estimate the strength of these bonds. Overall, this computational investigation provides an in-depth understanding on the preferential selectivity of the ligand with An(III) over Ln(III) using DFT calculations.
AB - Separation of trivalent actinides An(III) from lanthanide Ln(III) is an extremely challenging task in handling nuclear wastes due to their similar chemical behaviours. Though many designed organic ligands have been used for the separation of Ln(III) from An(III) over the years, selectivity and efficiency is still a matter of concern. This drives us to formulate new efficient ligands, in which mixed –N, –O donor ligands are one of the most emerging and promising agents in separation of An(III) from Ln(III). In this work, recently reported TMPhenDA ligand has been investigated for their complexation behaviour with An(III) (U, Am, Cm) and Ln(III) (Nd, Eu, Gd) ions using scalar relativistic ZORA/DFT calculations. Computed bond parameters show that the An(III) ions bind strongly to the ligand than the lanthanide ions. Bond order and QTAIM analyses have been done on the optimized geometries to understand the bonding situation present in the M3+TMPhenDA complexes. Further, energy decomposition analysis is taken up to assign the percentage covalency of M-N and M-O bonds in these complexes to estimate the strength of these bonds. Overall, this computational investigation provides an in-depth understanding on the preferential selectivity of the ligand with An(III) over Ln(III) using DFT calculations.
KW - Lanthanide-actinide separation
KW - M-N/M-O bonding nature
KW - Nuclear waste management
KW - Scalar relativistic DFT
UR - http://www.scopus.com/inward/record.url?scp=85102371083&partnerID=8YFLogxK
U2 - 10.1016/j.molliq.2021.115819
DO - 10.1016/j.molliq.2021.115819
M3 - Article
AN - SCOPUS:85102371083
SN - 0167-7322
VL - 332
JO - Journal of Molecular Liquids
JF - Journal of Molecular Liquids
M1 - 115819
ER -