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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model
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Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model

机译：铜（II）的水合：密度泛函理论和COSMO溶剂化模型的新见解

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摘要

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_(x~2-y~2) 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.
机译：Cu（II）离子的水合结构一直是文献中不断争论的主题。在本文中，我们使用密度泛函理论（B3LYP）和COSMO连续介质溶剂模型来表征[Cu（H2O）_n]〜（2+）团簇的结构和稳定性，其为配位数（4、5和6）和簇大小（n = 4-18）。我们发现气相中热力学最受青睐的Cu（II）配合物具有非常开放的四坐标结构。它们是由稳定的方形平面[Cu（H2O）8]〜（2+）核形成的，该核通过在Cu（II）离子d_（x〜2-y〜2）轨道中的不成对电子而稳定。这与最近的质谱实验所建议的团簇几何形状是一致的。在水相中，我们发现较紧凑的五坐标方锥几何比四坐标或六坐标簇更稳定，这与最近对Cu（II）水溶液进行的EXAFS和XANES组合研究相一致。但是，在金属离子周围有两个完全水化壳的五坐标和六坐标模型之间的小能量差异（〜1.4 kcal / mol）表明溶液中可能同时存在这两种形式。

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