Signatures of Size-Dependent Structural Patterns in Hydrated Copper(I) Clusters, Cu+(H2O)n=1–10

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• 作者：Jonathan D. Herr ; Ryan P. Steele
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：December 29, 2016
• 年：2016
• 卷：120
• 期：51
• 页码：10252-10263
• 全文大小：591K
• ISSN：1520-5215

文摘

The isomers of a hydrated Cu(I) ion with n = 1–10 water molecules were investigated by using ab initio quantum chemistry and an automated isomer-search algorithm. The electronic structure and vibrational spectra of the hundreds of resulting isomers were used to analyze the source of the observed bonding patterns. A structural evolution from dominantly two-coordinate structures (n = 1–4) toward a mixture of two- and three-coordinate structures was observed at n = 5–6, where the stability provided by expanded hydrogen-bonding was competitive with the dominantly electrostatic interaction between the water ligand and remaining binding sites of the metal ion. Further hydration (n = 7–10) led to a mixture of three- and four-coordinate structures. The metal ion was found, through spectroscopic signatures, to appreciably perturb the O–H bonds of even third-shell water molecules, which highlighted the ability of this nominally simple ion to partially activate the surrounding water network.