Universität zu Köln

Dolg, Michael ORCID: 0000-0002-0538-0837, Cao, Xiaoyan ORCID: 0000-0002-3438-575X and Ciupka, Jan (2014). Misleading evidence for covalent bonding from (EuX)-X-III and (AmX)-X-III density functional theory bond lengths. J. Electron Spectrosc. Relat. Phenom., 194. S. 8 - 14. AMSTERDAM: ELSEVIER SCIENCE BV. ISSN 1873-2526

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Abstract

In complexes of trivalent Eu and Am standard unrestricted Kohn-Sham density functional calculations tend to yield shorter bond distances for the Am-X than for the Eu-X bonds, especially when X is a so called soft ligand. Since the ionic radius of Am-III is larger than the one of Eu-III the reversed order of the bond distances is sometimes explained by a higher covalency of the Am-X bond compared to the one of the Eu-X bond. A comparison of density functional with wavefunction-based correlated calculations for several model systems reveals, however, that the energetically low-lying and spatially compact 4f shell of Eu-III often is erroneously filled with significantly more than 6 electrons at the density functional theory level, thus yielding considerably too long bond distances. Particularly claims based on comparisons of structures optimized at the density functional level that the strong preference of the Cyanex 301 ligand for Am-III over Eu-III is due to an increased covalency in the Am-S bonds should be viewed with some reservation. (C) 2013 Elsevier B.V. All rights reserved.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED Cao, Xiaoyan UNSPECIFIED orcid.org/0000-0002-3438-575X UNSPECIFIED Ciupka, Jan UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-437532
DOI:	10.1016/j.elspec.2013.07.004
Journal or Publication Title:	J. Electron Spectrosc. Relat. Phenom.
Volume:	194
Page Range:	S. 8 - 14
Date:	2014
Publisher:	ELSEVIER SCIENCE BV
Place of Publication:	AMSTERDAM
ISSN:	1873-2526
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 ENERGY-ADJUSTED PSEUDOPOTENTIALS; VALENCE BASIS-SETS; GENERALIZED GRADIENT APPROXIMATION; RARE-EARTH-ELEMENTS; PURIFIED CYANEX 301; GAUSSIAN-BASIS SETS; AB-INITIO; DITHIOPHOSPHINIC ACIDS; TRIVALENT ACTINIDE; ATOMS LI Multiple languages Spectroscopy Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/43753