Simulation of the chemical interactions of luminescent lanthanide complexes series [Ln(cin)₃(H₂O)₃]·Hcin and [Ln₂(cin)₆(bpy)₂] using DFT calculations

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• 作者：Mateus J.F. Martins^a ; Lippy F. Marques^b ; Sé ; rgio R. Tavares^c ; Flá ; via C. Machado^c ; Welber G. Quirino^a ; Alexandre A. Leitã ; o^c ; ^{alexandre.leitao@ufjf.edu.br" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Lanthanides ; Computational simulation ; Ab initio calculations ; PBE ; PBE-D2 ; GGA  ; +  ; U
• 刊名：Computational Materials Science
• 出版年：2016
• 出版时间：1 April 2016
• 年：2016
• 卷：115
• 期：Complete
• 页码：184-191
• 全文大小：2816 K

文摘

In this work, DFT calculations were conducted to understand the interactions of two luminescent complexes series, named [Ln(cin)₃(H₂O)₃]·Hcin and the [Ln₂(cin)₆(bpy)₂] (where cin = hydrocinnamate anion and bpy = 2,2′-bipyridine). For the reduction of the computational cost in the geometry optimization calculations, the PBE-D2 and the GGA + U methodologies were tested, even as the 4f electrons treatment, in the core and in the valence shell of the lanthanide metals.

As a result of the electronic structure calculations, the lattice parameters of these complexes was obtained and corroborated by a comparison between the simulated and experimental diffractograms. The projected density of states and the charge density analysis were made for a better understanding of the electronic structure and the stabilization of these complexes, like the importance of some ligands and the difference of the interaction between the rare-earth metals and the ligands.

It could be concluded that there is no need to compute the spin polarization and to include the hubbard correction in order to conduct a structural analysis of these rare-earth metal complexes. The electronic density maps show that the structures are mainly stabilized by charge transfer between the ligands and the rare-earth cations. This result also corroborates the geometry optimizations performed with the DFT-D2 method, which indicate that the computation of the Van der Waals forces are negligible.