Hydration of copper(II): New insights from density functional theory and the COSMO solvation model

Vyacheslav S. Bryantsev, Mamadou S. Diallo, Adri C.T. Van Duin, William A. Goddard

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94 Scopus citations


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 dx2-y2 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 (∼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.

Original languageEnglish (US)
Pages (from-to)9104-9112
Number of pages9
JournalJournal of Physical Chemistry A
Issue number38
StatePublished - Sep 25 2008

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry


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