On The Density Functional Theory Treatment of Lanthanide Coordination Compounds: A Comparative Study in a Series of Cu-Ln (Ln = Gd, Tb, Lu) Binuclear Complexes
| Autor: | Marilena Ferbinteanu, Marco Scarrozza, Dan Maftei, Fanica Cimpoesu, Bogdan Frecus, Alessandro Stroppa, Ionel Humelnicu |
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| Rok vydání: | 2017 |
| Předmět: |
Ligand field theory
Lanthanide chemistry.chemical_classification 010405 organic chemistry Chemistry 010402 general chemistry 01 natural sciences 0104 chemical sciences Coordination complex Inorganic Chemistry Crystallography Atomic orbital Computational chemistry Density functional theory Molecular orbital Physical and Theoretical Chemistry Ground state Multiplet |
| Zdroj: | Inorganic chemistry. 56(16) |
| ISSN: | 1520-510X |
| Popis: | The nontrivial aspects of electron structure in lanthanide complexes, considering ligand field (LF) and exchange coupling effects, have been investigated by means of density functional theory (DFT) calculations, taking as a prototypic case study a series of binuclear complexes [LCu(O2COMe)Ln(thd)2], where L2– = N,N′-2,2-dimethyl-propylene-di(3-methoxy-salicylidene-iminato) and Ln = Tb, Lu, and Gd. Particular attention has been devoted to the Cu–Tb complex, which shows a quasi-degenerate nonrelativistic ground state. Challenging the limits of density functional theory (DFT), we devised a practical route to obtain different convergent solutions, permuting the starting guess orbitals in a manner resembling the run of the β electron formally originating from the f8 configuration of the Tb(III) over seven molecular orbitals (MOs) with predominant f-type character. Although the obtained states cannot be claimed as the DFT computed split of the 7F multiplet, the results are yet interesting numeric experiments, r... |
| Databáze: | OpenAIRE |
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