Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.
J Chem Phys. 2010 Jan 7;132(1):011101. doi: 10.1063/1.3285266.
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.
使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顺序对纯交换函数或混合交换函数的选择非常敏感。实验和计算光谱的比较表明，该团簇具有密堆积的双帽八面体结构，与最近对中性团簇的立方结构的预测形成对比。我们的研究结果表明，在应用于铑团簇时，通过混合函数，在 DFT 计算中包含一些精确交换贡献的重要性，并对一般情况下用于后过渡金属团簇的纯函数的应用提出了质疑。
