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Electronic Structures of Highly Symmetrical Compounds of f Elements 44 [1]. First Parametric Analysis of the Absorption Spectrum of a Molecular Compound of Tervalent Uranium: Tris[hydrotris(1‐pyrazolyl)borato]uranium(III)
Author(s) -
Apostolidis Christos,
Morgenstern Alfred,
Rebizant Jean,
Kanellakopulos Basil,
Walter Olaf,
Powietzka Bernhard,
Karbowiak Miroslav,
Reddmann Hauke,
Amberger HannsDieter
Publication year - 2010
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.200900271
Subject(s) - chemistry , spectrochemical series , hamiltonian (control theory) , ligand field theory , molecular orbital , wave function , absorption spectroscopy , uranium , spectral line , physics , atomic physics , molecule , quantum mechanics , mathematical optimization , mathematics , organic chemistry , nuclear physics
The absorption spectrum of tris[hydrotris(1‐pyrazolyl)borato]uranium(III) (UTp 3 ) was run at room and low temperatures. From the spectra obtained, a truncated crystal field (CF) splitting pattern could be derived, and simulated by fitting the free parameters of a phenomenological Hamiltonian achieving an r.m.s. deviation of 37.7 cm –1 for 29 assignments. The parameters used allow the insertion of the Tp ligand into empirical spectrochemical, nephelauxetic and relativistic nephelauxetic series of U III compounds, and the set‐up of experimentally based nonrelativistic and relativistic molecular orbital schemes of UTp 3 in the f range. Using the wavefunctions and eigenvalues of the fit, the experimentally determined temperature dependence (in the range 1.34–294.4 K) of μ 2 eff could be reproduced adopting an orbital reduction factor k = 0.99.