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Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model

Bryantsev, Vyacheslav S. and Diallo, Mamadou S. and van Duin, Adri C. T. and Goddard, William A., III (2008) Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model. Journal of Physical Chemistry A, 112 (38). pp. 9104-9112. ISSN 1089-5639. doi:10.1021/jp804373p.

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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 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.

Item Type:Article
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URLURL TypeDescription
Diallo, Mamadou S.0000-0002-2571-1568
van Duin, Adri C. T.0000-0002-3478-4945
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2008 American Chemical Society. Received: May 17, 2008. Revised Manuscript Received: July 22, 2008. Web Release Date: September 3, 2008. Funding for this work was provided by the National Science Foundation (NIRT CTS Award # 0506951) and by the US Environmental Protection Agency (STAR Grant RD-83252501). The computational facilities used in these studies were funded by grants from ARO-DURIP, ONR-DURIP and NSF-MRI. Supporting Information Available: Cartesian coordinates and absolute energies for all [Cu(H2O)n]2+ complexes optimized at the B3LYP/6-311++G(d,p) level of theory. This material is available free of charge via the Internet at
Funding AgencyGrant Number
Environmental Protection Agency (EPA)RD-83252501
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:38
Record Number:CaltechAUTHORS:BRYjpca08
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11955
Deposited By: Archive Administrator
Deposited On:14 Oct 2008 00:45
Last Modified:08 Nov 2021 22:23

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