Original paper

Journal of Molecular Modeling

, Volume 12, Issue 4, pp 373-389

First online:

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

  • Ricardo O. FreireAffiliated withDepartamento de Química Fundamental, Universidade Federal de Pernambuco
  • , Gerd B. RochaAffiliated withDepartamento de Química Fundamental, Universidade Federal de Pernambuco
  • , Alfredo M. SimasAffiliated withDepartamento de Química Fundamental, Universidade Federal de Pernambuco Email author 

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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