Please use this identifier to cite or link to this item: https://doi.org/10.1002/chem.201605102
Title: Ab Initio Crystal Field for Lanthanides
Authors: Ungur, Liviu 
Chibotaru, Liviu F
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
ab initio calculations
covalent interactions
electrostatic models
lanthanides
single-molecule magnets
SINGLE-MOLECULE MAGNETS
ANGULAR OVERLAP MODEL
MULTICONFIGURATIONAL PERTURBATION-THEORY
LIGAND-FIELD
ELECTROSTATIC MODEL
ION MAGNETS
WAVE-FUNCTIONS
BASIS-SETS
COMPLEXES
MONONUCLEAR
Issue Date: 1-Mar-2017
Publisher: WILEY-V C H VERLAG GMBH
Citation: Ungur, Liviu, Chibotaru, Liviu F (2017-03-01). Ab Initio Crystal Field for Lanthanides. CHEMISTRY-A EUROPEAN JOURNAL 23 (15) : 3708-3718. ScholarBank@NUS Repository. https://doi.org/10.1002/chem.201605102
Abstract: An ab initio methodology for the first-principle derivation of crystal-field (CF) parameters for lanthanides is described. The methodology is applied to the analysis of CF parameters in [Tb(Pc)2]‑(Pc=phthalocyanine) and Dy4K2([Dy4K2O(OtBu)12]) complexes, and compared with often used approximate and model descriptions. It is found that the application of geometry symmetrization, and the use of electrostatic point-charge and phenomenological CF models, lead to unacceptably large deviations from predictions based on ab initio calculations for experimental geometry. It is shown how the predictions of standard CASSCF (Complete Active Space Self-Consistent Field) calculations (with 4f orbitals in the active space) can be systematically improved by including effects of dynamical electronic correlation (CASPT2 step) and by admixing electronic configurations of the 5d shell. This is exemplified for the well-studied Er-trensal complex (H3trensal=2,2’,2“-tris(salicylideneimido)trimethylamine). The electrostatic contributions to CF parameters in this complex, calculated with true charge distributions in the ligands, yield less than half of the total CF splitting, thus pointing to the dominant role of covalent effects. This analysis allows the conclusion that ab initio crystal field is an essential tool for the decent description of lanthanides.
Source Title: CHEMISTRY-A EUROPEAN JOURNAL
URI: https://scholarbank.nus.edu.sg/handle/10635/228799
ISSN: 0947-6539
1521-3765
DOI: 10.1002/chem.201605102
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