Premium
Zur Elektronenstruktur metallorganischer Komplexe der f‐Elemente. 67 Erstmalige parametrische Analyse des Absorptionsspektrums einer Molekülverbindung des Ce III μ: Tris(η 5 ‐tetramethylcyclopentadienyl)cer
Author(s) -
Amberger HannsDieter,
Reddmann Hauke
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700353
Subject(s) - chemistry , cerium , ion , absorption spectroscopy , spectral line , hamiltonian (control theory) , atomic physics , crystallography , inorganic chemistry , physics , mathematical optimization , mathematics , organic chemistry , quantum mechanics , astronomy
Electronic Structures of Organometallic Complexes of f Elements. 67 First Parametric Analysis of the Absorption Spectrum of a Molecular Compound of Ce III μ: Tris(η 5 ‐tetramethylcyclopentadienyl)cerium(III) The absorption spectra (in the IR/NIR/Vis/UV range) of Ce(C 5 Me 4 H) 3 ( 1 ) and La(C 5 Me 4 H) 3 ( 2 ) were recorded at room and low temperatures. From the spectra obtained, two alternative closely related crystal field (CF) splitting patterns of 1 could be derived, and simulated by fitting the free parameters of a phenomenological Hamiltonian. The fact that the difference of the experimental energies of the barycenters of CF levels of the multiplets 2 F 7/2 and 2 F 5/2 is larger than in the gaseous free Ce 3+ ion (“anti”‐relativistic nephelauxetic effect) could be explained by coupling effects of these multiplets via the CF, resulting in lower spin‐orbit coupling parameters than in the case of the gaseous free Ce 3+ ion. The experimentally derived CF splitting pattern of 1 is compared with the predictions of previous non‐relativistic SW‐Xα and relativistic DV‐Xα calculations.