Universität zu Köln

Sadhu, Biswajit, Dolg, Michael ORCID: 0000-0002-0538-0837 and Kulkarni, Mukund S. (2020). Periodic trends and complexation chemistry of tetravalent actinide ions with a potential actinide decorporation agent 5-LIO(Me-3,2-HOPO): A relativistic density functional theory exploration. J. Comput. Chem., 41 (15). S. 1427 - 1436. HOBOKEN: WILEY. ISSN 1096-987X

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Abstract

A relativistic density functional theory (DFT) study is reported which aims to understand the complexation chemistry of An(4+) ions (An = Th, U, Np, and Pu) with a potential decorporation agent, 5-LIO(Me-3,2-HOPO). The calculations show that the periodic change of the metal binding free energy has an excellent correlation with the ionic radii and such change of ionic radii also leads to the structural modulation of actinide-ligand complexes. The calculated structural and binding parameters agree well with the available experimental data. Atomic charges derived from quantum theory of atoms in molecules (QTAIM) and natural bond order (NBO) analysis shows the major role of ligand-to-metal charge transfer in the stability of the complexes. Energy decomposition analysis, QTAIM, and electron localization function (ELF) predict that the actinide-ligand bond is dominantly ionic, but the contribution of orbital interaction is considerable and increases from Th4+ to Pu4+. A decomposition of orbital contributions applying the extended transition state-natural orbital chemical valence method points out the significant pi-donation from the oxygen donor centers to the electron-poor actinide ion. Molecular orbital analysis suggests an increasing trend of orbital mixing in the context of 5f orbital participation across the tetravalent An series (Th-Pu). However, the corresponding overlap integral is found to be smaller than in the case of 6d orbital participation. An analysis of the results from the aforementioned electronic structure methods indicates that such orbital participation possibly arises due to the energy matching of ligand and metal orbitals and carries the signature of near-degeneracy driven covalency.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Sadhu, Biswajit UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED Kulkarni, Mukund S. UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-341554
DOI:	10.1002/jcc.26186
Journal or Publication Title:	J. Comput. Chem.
Volume:	41
Number:	15
Page Range:	S. 1427 - 1436
Date:	2020
Publisher:	WILEY
Place of Publication:	HOBOKEN
ISSN:	1096-987X
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Theoretical Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ZETA VALENCE QUALITY; NATURAL-POPULATION; BASIS-SETS; ENERGY; PLUTONIUM; 3,4,3-LI(1,2-HOPO); APPROXIMATION; HYDROLYSIS; COVALENCY; EFFICIENT Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/34155