Communications: The structure of Rh(8) (+) in the gas phase.
Communications: The structure of Rh(8) (+) in the gas phase.
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DOI：
10.1063/1.3285266
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发表时间：
2009-09
期刊：
影响因子：
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通讯作者：
D. Harding;T. Walsh;S. M. Hamilton;W. Hopkins;S. Mackenzie;P. Gruene;M. Haertelt;G. Meijer;A. Fielicke
中科院分区：
文献类型：
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作者：
D. Harding;T. Walsh;S. M. Hamilton;W. Hopkins;S. Mackenzie;P. Gruene;M. Haertelt;G. Meijer;A. Fielicke
采用远红外多光子解离光谱和密度泛函理论（DFT）计算相结合的方法研究了Rh(8)（+）阳离子的几何结构。发现不同结构基序的能量排序敏感地依赖于纯交换官能团或混合交换官能团的选择。实验光谱和计算光谱的比较表明，该星团具有紧密堆积的二头八面体结构，这与最近中性星团的立方结构的预测相反。我们的研究结果表明，当应用于铑团簇时，通过混合泛函在DFT计算中包括一些精确的交换贡献的重要性，并对纯泛函在一般晚过渡金属团簇中的应用提出了质疑。
The geometric structure of the Rh(8) (+) cation is investigated using a combination of far-infrared multiple photon dissociation spectroscopy and density functional theory (DFT) calculations. The energetic ordering of the different structural motifs is found to depend sensitively on the choice of pure or hybrid exchange functionals. Comparison of experimental and calculated spectra suggests the cluster to have a close-packed, bicapped octahedral structure, in contrast to recent predictions of a cubic structure for the neutral cluster. Our findings demonstrate the importance of including some exact exchange contributions in the DFT calculations, via hybrid functionals, when applied to rhodium clusters, and cast doubt on the application of pure functionals for late transition metal clusters in general.