Universität zu Köln

Cao, Xiaoyan ORCID: 0000-0002-3438-575X, Heidelberg, Daniel, Ciupka, Jan and Dolg, Michael ORCID: 0000-0002-0538-0837 (2010). First-Principles Study of the Separation of Am-III/Cm-III from Eu-III with Cyanex301. Inorg. Chem., 49 (22). S. 10307 - 10316. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-510X

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Abstract

The experimentally observed extraction complexes of trivalent lanthanide Eu-III and actinide Am-III/Cm-III cations with purified Cyanex301 [bis(2,4,4-trimethylpentyl)dithiophosphinic acid, HBTMPDTP denoted as HL], i.e., ML3 (M = Eu, Am, Cm) as well as the postulated complexes HAmL4 and HEuL4(H2O) have been studied by using energy-consistent 4f- and 5f-in-core pseudopotentials for trivalent f elements, combined with density functional theory and second-order Moller-Plesset perturbation theory. Special attention was paid to explaining the high selectivity of Cyanex301 for Am-III/Cm-III over Eu-III. It is shown that the neutral complexes ML3, where L acts as a bidentate ligand and the metal cation is coordinated by six S atoms, are most likely the most stable extraction complexes. The calculated metal-sulfur bond distances for ML3 do reflect the cation employed: i.e., the larger the cation, the longer the metal-sulfur bond distances. The calculated M-S and M-P bond lengths agree very well with the available experimental data. The obtained changes of the Gibbs free energies in the extraction reactions M3+ + 3HL -> ML3 + 3H(+) agree with the thermodynamical priority for Am3+ and Cm3+. Moreover, the ionic metal-ligand dissociation energies of the extraction complexes ML3 show that, although EuL3 is the most stable complex in the gas phase, it is the least stable in aqueous solution.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Cao, Xiaoyan UNSPECIFIED orcid.org/0000-0002-3438-575X UNSPECIFIED Heidelberg, Daniel UNSPECIFIED UNSPECIFIED UNSPECIFIED Ciupka, Jan UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-492481
DOI:	10.1021/ic100844t
Journal or Publication Title:	Inorg. Chem.
Volume:	49
Number:	22
Page Range:	S. 10307 - 10316
Date:	2010
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-510X
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language CONSISTENT 5F-IN-CORE PSEUDOPOTENTIALS; ENERGY-ADJUSTED PSEUDOPOTENTIALS; AB-INITIO PSEUDOPOTENTIALS; DENSITY-FUNCTIONAL THEORY; ABSORPTION FINE-STRUCTURE; ZETA-VALENCE QUALITY; GAUSSIAN-BASIS SETS; LANTHANIDE CATIONS; TRIVALENT ACTINIDE; BIS(2,4,4-TRIMETHYLPENTYL)DITHIOPHOSPHINIC ACID Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/49248