Structural, energetic, and electronic properties of La(III)-dimethyl sulfoxide clusters.

By using accurate density functional theory calculations, we have studied the cluster complexes of a La(3+) ion interacting with a small number of dimethyl sulfoxide (DMSO) molecules of growing size (from 1 to 12). Extended structural, energetic, and electronic structure analyses have been performed to provide a complete picture of the physical properties that are the basis of the interaction of La(III) with DMSO. Recent experimental data in the solid and liquid phase have suggested a coordination number of 8 DMSO molecules with a square antiprism geometry arranged similarly in the liquid and crystalline phases. By using a cluster approach on the La(3+)(DMSO)n gas phase isolated structures, we have found that the 8-fold geometry, albeit less regular than in the crystal, is probably the most stable cluster. Furthermore, we provide new evidence of a 9-fold complexation geometric arrangement that is competitive (at least energetically) with the 8-fold one and that might suggest the existence of transient structures with higher coordination numbers in the liquid phase.