期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 112, 期 38, 页码 9104-9112出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp804373p
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资金
- National Science Foundation [0506951]
- US Environmental Protection Agency [RD-83252501]
- ARO-DURIP
- ONR-DURIP
- NSF-MRI
- Directorate For Engineering
- Div Of Chem, Bioeng, Env, & Transp Sys [0506951] Funding Source: National Science Foundation
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.
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