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

被引:24
作者
Ferbinteanu, Marilena [1 ]
Stroppa, Alessandro [2 ,3 ,4 ]
Scarrozza, Marco [2 ]
Humelnicu, Ionel [5 ]
Maftei, Dan [5 ]
Frecus, Bogdan [6 ]
Cimpoesu, Fanica [6 ]
机构
[1] Univ Bucharest, Dept Inorgan Chem, Dumbrava Rosie 23, Bucharest 020462, Romania
[2] CNR, SPIN Inst, I-67100 Laquila, Italy
[3] Shanghai Univ, Int Ctr Quantum & Mol Struct, 99 Shangda Rd, Shanghai 200444, Peoples R China
[4] Shanghai Univ, Dept Phys, 99 Shangda Rd, Shanghai 200444, Peoples R China
[5] Alexandru Ioan Cuza Univ, Phys & Theoret Chem Dept, 11 Bd Carol 1, Iasi 700506, Romania
[6] Inst Phys Chem, Splaiul Independentei 202, Bucharest 060021, Romania
关键词
SINGLE-MOLECULE MAGNET; ANGULAR OVERLAP MODEL; COMPACT EFFECTIVE POTENTIALS; TRANSITION-METAL IONS; EXPONENT BASIS-SETS; II/GD-III COUPLE; POLYNUCLEAR COMPLEXES; EXCHANGE INTERACTION; DINUCLEAR COMPLEXES; INTRINSIC PROPERTY;
D O I
10.1021/acs.inorgchem.7b00587
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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 beta electron formally originating from the f(8) 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 F-7 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.
引用
收藏
页码:9474 / 9485
页数:12
相关论文
共 84 条
[1]   Introduction of n-electron valence states for multireference perturbation theory [J].
Angeli, C ;
Cimiraglia, R ;
Evangelisti, S ;
Leininger, T ;
Malrieu, JP .
JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (23) :10252-10264
[2]  
[Anonymous], 2001, CHEMISTS GUIDE DENSI
[3]   Elucidation of ligand-field theory.: Reformulation and revival by density functional theory [J].
Anthon, C ;
Bendix, J ;
Schäffer, CE .
OPTICAL SPECTRA AND CHEMICAL BONDING IN TRANSITION METAL COMPLEXES, 2004, 107 :207-301
[4]   Mimicking the two-dimensional spectrochemical series using density functional computations [J].
Anthon, C ;
Bendix, J ;
Schäffer, CE .
INORGANIC CHEMISTRY, 2004, 43 (24) :7882-7886
[5]   Periodic Trends in Lanthanide Compounds through the Eyes of Multireference ab Initio Theory [J].
Aravena, Daniel ;
Atanasov, Mihail ;
Neese, Frank .
INORGANIC CHEMISTRY, 2016, 55 (09) :4457-4469
[6]   A DFT based ligand field theory [J].
Atanasov, A ;
Daul, CA ;
Rauzy, C .
OPTICAL SPECTRA AND CHEMICAL BONDING IN INORGANIC COMPOUNDS, VOL 1, 2004, 106 :97-125
[7]   Ground states, excited states, and metal-ligand bonding in rare earth hexachloro complexes: A DFT-based ligand field study [J].
Atanasov, M ;
Daul, C ;
Gudel, HU ;
Wesolowski, TA ;
Zbiri, M .
INORGANIC CHEMISTRY, 2005, 44 (08) :2954-2963
[8]   New insights into the effects of covalency on the ligand field parameters: a DFT study [J].
Atanasov, M ;
Daul, CA ;
Rauzy, C .
CHEMICAL PHYSICS LETTERS, 2003, 367 (5-6) :737-746
[9]  
Baerends E.J., ADF2010 01
[10]   A Few Comments on the Application of Density Functional Theory to the Calculation of the Magnetic Structure of Oligo-Nuclear Transition Metal Clusters [J].
Bencini, Alessandro ;
Totti, Federico .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2009, 5 (01) :144-154