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Moossen, Oliver and Dolg, Michael ORCID: 0000-0002-0538-0837 (2016). Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis. J. Phys. Chem. A, 120 (22). S. 3966 - 3975. WASHINGTON: AMER CHEMICAL SOC. ISSN 1089-5639

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Abstract

The geometric and electronic structure of the recently experimentally studied molecules ZCeF(2) (Z = CH2, O) was investigated by density functional theory (DFT) and wave function-based ab initio methods. Special attention was paid to the Ce-Z metal-ligand bonding, especially to the nature of the interaction between the Ce 4f and the Z 2p orbitals and the possible multiconfigurational character arising from it, as well as to the assignment of an oxidation state of Ce reflecting the electronic structure. Complete active space self consistent field (CASSCF) calculations were performed, followed by orbital rotations in the active orbital space. The methylene compound CH2CeF2 has an open-shell singlet ground state, which is characterized by a two-configurational wave function in the basis of the strongly mixed natural CASSCF orbitals. The system can also be described in a very compact way by the dominant Ce 4f(1) C 2p(1) configuration, if nearly pure Ce 4f and C 2p orbitals are used. In the basis of these localized orbitals, the molecule is almost monoconfigurational and should be best described as a Ce(III) system. The singlet ground state of the oxygen OCeF2 complex is of closed-shell character when a monoconfigurational wave function with very strongly mixed Ce 4f and O 2p CASSCF natural orbitals is used for the description. The transformation to orbitals localized on the cerium and oxygen atoms leads to a multiconfigurational wave function and reveals characteristics of a mixed valent Ce(IV)/ Ce(III) compound. Additionally, the interactions of the localized active orbitals were analyzed by evaluating the expectation values of the charge fluctuation operator and the local spin operator. The Ce 4f and C 2p orbital interaction of the CH2CeF2 compound is weakly covalent and resembles the interaction of the H is orbitals in a stretched hydrogen dimer. In contrast, the interaction of the localized active orbitals for OCeF2 shows ionic character. Calculated vibrational Ce-C and Ce-O stretching frequencies at the DFT, CASSCF, second-order Rayleigh-Schrodinger perturbation theory (RS2C), multireference configuration interaction (MRCI), as well as single, doubles, and perturbative triples coupled cluster (CCSD(T)) level are reported and compared to experimental infrared absorption data in a Ne and Ar matrix.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Moossen, Oliver UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-272391
DOI:	10.1021/acs.jpca.6b03770
Journal or Publication Title:	J. Phys. Chem. A
Volume:	120
Number:	22
Page Range:	S. 3966 - 3975
Date:	2016
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1089-5639
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 ELECTRONIC-STRUCTURE CALCULATIONS; ZETA VALENCE QUALITY; CONFIGURATION-INTERACTION; BASIS-SETS; CORRELATION-ENERGY; GROUND-STATE; CEROCENE; CE; THERMOCHEMISTRY; APPROXIMATION Multiple languages Chemistry, Physical; Physics, Atomic, Molecular & Chemical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/27239