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

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 Gd(3+)(H(2)O) and Gd(3+)(NH(3)) 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.