DC Field | Value | Language |
---|---|---|
dc.contributor.author | Bryantsev, VS | ko |
dc.contributor.author | Diallo, Mamadou S | ko |
dc.contributor.author | van Duin, ACT | ko |
dc.contributor.author | Goddard, WA | ko |
dc.date.accessioned | 2013-03-07T12:05:53Z | - |
dc.date.available | 2013-03-07T12:05:53Z | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.issued | 2008-09 | - |
dc.identifier.citation | JOURNAL OF PHYSICAL CHEMISTRY A, v.112, no.38, pp.9104 - 9112 | - |
dc.identifier.issn | 1089-5639 | - |
dc.identifier.uri | http://hdl.handle.net/10203/90133 | - |
dc.description.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(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. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | ELECTRONIC-STRUCTURE CALCULATIONS | - |
dc.subject | MOLECULAR-DYNAMICS SIMULATIONS | - |
dc.subject | CONTINUUM DIELECTRIC THEORY | - |
dc.subject | TRANSITION-METAL CATIONS | - |
dc.subject | JAHN-TELLER INVERSION | - |
dc.subject | AMINO-ACID COMPLEXES | - |
dc.subject | ION-WATER CLUSTERS | - |
dc.subject | FREE-ENERGY | - |
dc.subject | AB-INITIO | - |
dc.subject | GAS-PHASE | - |
dc.title | Hydration of copper(II): New insights from density functional theory and the COSMO solvation model | - |
dc.type | Article | - |
dc.identifier.wosid | 000259341900029 | - |
dc.identifier.scopusid | 2-s2.0-53849126514 | - |
dc.type.rims | ART | - |
dc.citation.volume | 112 | - |
dc.citation.issue | 38 | - |
dc.citation.beginningpage | 9104 | - |
dc.citation.endingpage | 9112 | - |
dc.citation.publicationname | JOURNAL OF PHYSICAL CHEMISTRY A | - |
dc.identifier.doi | 10.1021/jp804373p | - |
dc.contributor.localauthor | Diallo, Mamadou S | - |
dc.contributor.nonIdAuthor | Bryantsev, VS | - |
dc.contributor.nonIdAuthor | van Duin, ACT | - |
dc.contributor.nonIdAuthor | Goddard, WA | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | ELECTRONIC-STRUCTURE CALCULATIONS | - |
dc.subject.keywordPlus | MOLECULAR-DYNAMICS SIMULATIONS | - |
dc.subject.keywordPlus | CONTINUUM DIELECTRIC THEORY | - |
dc.subject.keywordPlus | TRANSITION-METAL CATIONS | - |
dc.subject.keywordPlus | JAHN-TELLER INVERSION | - |
dc.subject.keywordPlus | AMINO-ACID COMPLEXES | - |
dc.subject.keywordPlus | ION-WATER CLUSTERS | - |
dc.subject.keywordPlus | FREE-ENERGY | - |
dc.subject.keywordPlus | AB-INITIO | - |
dc.subject.keywordPlus | GAS-PHASE | - |
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