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Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2017, 56, 16, 9474-9485
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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

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† Department of Inorganic Chemistry, University of Bucharest, Dumbrava Rosie 23, Bucharest 020462, Romania
‡ SPIN Institute of Consiglio Nazionale delle Ricerche, L’Aquila 67100, Italy
§ International Centre for Quantum and Molecular Structures, and Physics Department, Shanghai University, 99 Shangda Road, Shanghai, 200444 China
∥ Physical and Theoretical Chemistry Department, Alexandru Ioan Cuza University, 11 Bd. Carol I, 700506 Iasi, Romania
⊥ Institute of Physical Chemistry, Splaiul Independentei 202, Bucharest 060021, Romania
*E-mail: [email protected]
Cite this: Inorg. Chem. 2017, 56, 16, 9474–9485
Publication Date (Web):August 7, 2017
https://doi.org/10.1021/acs.inorgchem.7b00587
Copyright © 2017 American Chemical Society
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Abstract

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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, relevant for the ligand field effects. We also performed broken symmetry (BS) DFT estimation of exchange coupling in the Cu–Gd system, using different settings, with Gaussian-type and plane-wave bases, finding a good match with the coupling parameter from experimental data. We also caught BS-type states for each of the mentioned series of different states emulated for the Cu–Tb complex, finding almost equal exchange coupling parameters throughout the seven LF-like configurations, the magnitude of the J parameter being comparable with those of the Cu–Gd system.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b00587.

  • Used molecular geometry and computational methodologies illustrated in sample input files and commented keywords, further numeric experiments and considerations related with the plane-wave DFT+U calculations (PDF)

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