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

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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(x2-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 (similar to 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.
Publisher
AMER CHEMICAL SOC
Issue Date
2008-09
Language
English
Article Type
Article
Keywords

ELECTRONIC-STRUCTURE CALCULATIONS; MOLECULAR-DYNAMICS SIMULATIONS; CONTINUUM DIELECTRIC THEORY; TRANSITION-METAL CATIONS; JAHN-TELLER INVERSION; AMINO-ACID COMPLEXES; ION-WATER CLUSTERS; FREE-ENERGY; AB-INITIO; GAS-PHASE

Citation

JOURNAL OF PHYSICAL CHEMISTRY A, v.112, no.38, pp.9104 - 9112

ISSN
1089-5639
DOI
10.1021/jp804373p
URI
http://hdl.handle.net/10203/90133
Appears in Collection
EEW-Journal Papers(저널논문)
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