Universität zu Köln

Dolg, Michael ORCID: 0000-0002-0538-0837 and Moossen, Oliver (2015). Cerium oxidation state and covalent 4f-orbital contributions in the ground state of bis(eta(8)-pentalene)cerium. J. Organomet. Chem., 794. S. 17 - 23. LAUSANNE: ELSEVIER SCIENCE SA. ISSN 1872-8561

Full text not available from this repository.

Abstract

The sandwich complex bis(eta(8)-pentalene)cerium Ce(C8H6)(2) was investigated by relativistic quantum chemical ab initio methods and the nature of the interaction between the Ce 4f and ligand pi orbitals was analyzed. It is shown for a multi-configurational ground state wavefunction of the complete active space variety that by means of an orbital rotation in the space of the strongly interacting orbitals it is possible to generate nearly pure Ce 4f and ligand pi orbitals without changing the total energy. These orbitals are occupied by one electron each, leading to an open-shell 4f(1) pi(1) ground state configuration. The admixture of the energetically higher closed-shell 4f(0) pi(2) configuration leads to a singlet ground state, making the complex another example for a molecular analog of a Ce(III)-based lattice Kondo system. A further analysis using local spin and occupation number fluctuations in a two-electron two-orbital description reveals that the Ce 4f-ligand pi interaction corresponds to a significantly stretched covalent bond: orbital and configuration mixing coefficients as well as local spin and occupation number fluctuations are very similar to those of hydrogen dimer H-2 at an interatomic distance of about two times the equilibrium distance. (C) 2015 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 Moossen, Oliver UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-392526
DOI:	10.1016/j.jorganchem.2015.05.063
Journal or Publication Title:	J. Organomet. Chem.
Volume:	794
Page Range:	S. 17 - 23
Date:	2015
Publisher:	ELSEVIER SCIENCE SA
Place of Publication:	LAUSANNE
ISSN:	1872-8561
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 AB-INITIO; ELECTRONIC-STRUCTURE; SANDWICH COMPLEXES; CEROCENE; ENERGY; URANOCENE; THOROCENE; WAVE; TH; CE Multiple languages Chemistry, Inorganic & Nuclear; Chemistry, Organic Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/39252