Ultrasoft pseudopotentials for lanthanide solvation complexes: Core or valence character of the 4f electrons

Rodolphe Pollet (1) , C. Clavaguéra (1) , J.-P. Dognon (1)

1 LFP - URA 2453 - Laboratoire Francis PERRIN

The 4f electrons of lanthanides, because of their strong localization in the region around the nucleus, are traditionally included in a pseudopotential core. This approximation is scrutinized by optimizing the structures and calculating the interaction energies of Gd3+(H2O) and Gd3+(NH3) microsolvation complexes within plane wave Perdew-Burke-Ernzerhof calculations using ultrasoft pseudopotentials where the 4f electrons are included either in the core or in the valence space. Upon comparison to quantum chemical MP2 and CCSD(T) reference calculations it is found that the explicit treatment of the 4f electrons in the valence shell yields quite accurate results including the required small spin polarization due to ligand charge transfer with only modest computational overhead.

Mots clés: gadolinium compounds; solvation; pseudopotential methods; core levels; valence bands; exchange interactions (electron); electron spin polarisation; charge exchange

Domaines: Chimie théorique et/ou physique

Rodolphe Pollet, C. Clavaguéra, J.-P. Dognon. Ultrasoft pseudopotentials for lanthanide solvation complexes: Core or valence character of the 4f electrons. Journal of Chemical Physics, 2006, 124, pp.164103 - 1-6. ⟨10.1063/1.2191498⟩. ⟨hal-00083928⟩