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Ligand‐Field Strength and Symmetry‐Restricted Covalency in Cu II Complexes – a Near‐Edge X‐ray Absorption Fine Structure Spectroscopy and Time‐Dependent DFT Study
Author(s) -
Mangione Giulia,
Pandolfo Luciano,
Sambi Mauro,
Ligorio Giovanni,
Nardi Marco Vittorio,
Cossaro Albano,
Floreano Luca,
Casarin Maurizio
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500222
Subject(s) - chemistry , time dependent density functional theory , xanes , spectrochemical series , ligand field theory , atomic orbital , density functional theory , crystallography , molecular orbital , absorption spectroscopy , copper , spectroscopy , magnetic circular dichroism , absorption (acoustics) , molecular physics , atomic physics , computational chemistry , molecule , electron , spectral line , physics , ion , organic chemistry , quantum mechanics , astronomy , acoustics
The low‐lying empty orbitals of bis(acetylacetonato)copper have been probed by near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy at the Cu L 2,3 edges and time‐dependent density functional theory (TDDFT) calculations within the Tamm–Dancoff approximation (TDA) coupled to the relativistic zeroth‐order regular approximation including spin–orbit effects (SO‐ZORA TDDFT‐TDA). Both the relative positions of NEXAFS features and their linear dichroism are satisfactorily reproduced. Moreover, a comparison with literature data pertaining to two other square‐planar Cu II complexes ([CuCl 4 ] 2– and copper phthalocyanine) provided information about how metal‐to‐ligand charge‐transfer transitions associated with excitations from Cu II 2p orbitals to low‐lying, ligand‐based π* molecular orbitals in a simplified one‐electron picture may contribute to the Cu II L 2,3 edge intensity and, thus, weaken its believed relationship with the Cu II –ligand symmetry‐restricted covalency.