Phys Chem Chem Phys. 2010 Oct 28;12(40):13215-23. doi: 10.1039/c0cp00639d. Epub 2010 Aug 27.

Computational study of lanthanide(III) hydration.

Physical chemistry chemical physics : PCCP

Jan Ciupka, Xiaoyan Cao-Dolg, Jonas Wiebke, Michael Dolg

PMID: 20820581 DOI: 10.1039/c0cp00639d

Abstract

Lanthanide(iii) hydration was studied by utilizing density-functional theory and second-order Møller-Plesset perturbation theory combined with scalar-relativistic 4f-in-core pseudopotentials and valence-only basis sets for the Ln(iii) ions. For [Ln(iii)(H(2)O)(h)](3+) (h = 7, 8, 9) and [Ln(iii)(H(2)O)(h-1)·H(2)O](3+) (h = 8, 9) molecular structures, binding energies, entropies and energies of hydration as well as Gibbs free energies of hydration were calculated using (8s7p6d3f2g)/[6s5p5d3f2g] basis sets for Ln(iii) and aug-cc-pV(D,T)Z basis sets for O and H in combination with the COSMO solvation model. At the generalized gradient approximation level of density-functional theory a preferred hydration number of 8 is found for La(iii)-Tm(iii) and 7 for Yb(iii)-Lu(iii), whereas hybrid density-functional theory predicts a hydration number 8 for all Ln(iii). At the SCS-MP2 level of theory the preferred hydration number is found to be 9 for La(iii)-Sm(iii) and 8 for Eu(iii)-Lu(iii) in good agreement with experimental evidence.

Publication Types

• Journal Article