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DFT Description of the Electronic Structure and Spectromagnetic Properties of Strongly Correlated Electronic Systems: Ni II , Cu II and Zn II o ‐Dioxolene Complexes
Author(s) -
Bencini Alessandro,
Carbonera Chiara,
Totti Federico
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305420
Subject(s) - chemistry , atomic orbital , electronic structure , copper , complete active space , density functional theory , zinc , electron configuration , perturbation theory (quantum mechanics) , computational chemistry , transition metal , atomic physics , crystallography , physics , ion , quantum mechanics , electron , basis set , organic chemistry , biochemistry , catalysis
The spectroscopic and magnetic properties of dioxolene complexes of zinc, copper and nickel were studied by DFT calculations on model complexes of formulas [(NH 3 ) 4 M II (SQ)] + (M=Zn, Ni; SQ=semiquinonato) and [(NH 3 ) 2 Cu II (SQ)] + . Standard approaches such as time‐dependent DFT (TDDFT), the Slater transition state (STS), and broken symmetry (BS) were found to be unable to completely account for the physical properties of the systems, and complete active space‐configuration interaction (CAS‐CI) calculations based on the Kohn–Sham (KS) orbitals was applied. The CAS‐CI energies, properly corrected with multireference perturbation theory (MR‐PT), were found to be in good agreement with experimental data. We present here a calculation protocol that has a low CPU cost/accuracy ratio and seems to be very promising for interpreting the properties of strongly correlated electronic systems in complexes of real chemical size.