title: Hydration of copper(II): new insights from density functional theory and the COSMO solvation model.
abstract: The hydrated structure of the Cu(II) ion has been a subject of ongoing debate in the literature. In this article, we use density functional theory (B3LYP) and the COSMO continuum solvent model to characterize the structure and stability of [Cu(H2O)n](2+) clusters as a function of coordination number (4, 5, and 6) and cluster size (n = 4-18). We find that the most thermodynamically favored Cu(II) complexes in the gas phase have a very open four-coordinate structure. They are formed from a stable square-planar [Cu(H2O)8](2+) core stabilized by an unpaired electron in the Cu(II) ion d(x(2)-y(2)) orbital. This is consistent with cluster geometries suggested by recent mass-spectrometric experiments. In the aqueous phase, we find that the more compact five-coordinate square-pyramidal geometry is more stable than either the four-coordinate or six-coordinate clusters in agreement with recent combined EXAFS and XANES studies of aqueous solutions of Cu(II). However, a small energetic difference (approximately 1.4 kcal/mol) between the five- and six-coordinate models with two full hydration shells around the metal ion suggests that both forms may coexist in solution.
authors.affiliation: Materials and Process Simulation Center, Beckman Institute 139-74, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Vyacheslav S
authors.initials: VS
authors.lastname: Bryantsev
authors.forename: Mamadou S
authors.initials: MS
authors.lastname: Diallo
authors.forename: Adri C T
authors.initials: AC
authors.lastname: van Duin
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard