Journal of Molecular Modeling

, Volume 12, Issue 4, pp 373–389 | Cite as

Lanthanide complex coordination polyhedron geometry prediction accuracies of ab initio effective core potential calculations

  • Ricardo O. Freire
  • Gerd B. Rocha
  • Alfredo M. Simas
Original paper


The ability to efficiently and accurately predict solid-state geometries of lanthanide coordination compounds efficiently and accurately is central for the design of new ligands capable of forming stable and highly luminescent complexes. Accordingly, we present in this paper a report on the capability of various ab initio effective core potential calculations in reproducing the coordination polyhedron geometries of lanthanide complexes. Starting with all combinations of HF, B3LYP and MP2(Full) with STO-3G, 3-21G, 6-31G, 6-31G* and 6-31+G basis sets for [Eu(H2O)9]3+ and closing with more manageable calculations for the larger complexes, we computed the fully predicted ab initio geometries for a total of 80 calculations on 52 complexes of Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III) and Tm(III), the largest containing 164 atoms. Our results indicate that RHF/STO-3G/ECP appears to be the most efficient model chemistry in terms of coordination polyhedron crystallographic geometry predictions from isolated lanthanide complex ion calculations. Moreover, both augmenting the basis set and/or including electron correlation generally enlarged the deviations and aggravated the quality of the predicted coordination polyhedron crystallographic geometry. Our results further indicate that Cosentino et al.’s suggestion of using RHF/3-21G/ECP geometries appears to be indeed a more robust, but not necessarily, more accurate recommendation to be adopted for the general lanthanide complex case.


Graphical visualization of unsigned mean errors, UME(Eu-L)s, involving only the interatomic distances between the europium central ion and the oxygen atoms of the coordination polyhedron of the cation nona-aqua-europium(III) for various model chemistries, all compared to the “Cambridge Structural Database 2004” crystallographic geometry


Lanthanide Rare-earth Ab initio ECP 



We appreciate the financial support from CNPq, CAPES (Brazilian agencies), and Grants from Instituto do Milênio de Materiais Complexos, FACEPE (Programa Primeiros Projetos) and Construção do Conhecimento por Agrupamento de Dados (CoCADa). We also wish to thank CENAPAD (Centro Nacional de Processamento de Alto Desempenho) at Campinas, Brazil, for having made available to us their computational facilities Finally, we gratefully acknowledge the Cambridge Crystallographic Data Centre for the Cambridge Structural Database.


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Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • Ricardo O. Freire
    • 1
  • Gerd B. Rocha
    • 1
  • Alfredo M. Simas
    • 1
  1. 1.Departamento de Química FundamentalUniversidade Federal de PernambucoRecifeBrazil

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