Gold nanoclusters are attractive because of their electronic and optical properties. Many theoretical models have been proposed to explain their electronic structures through an electron-counting approach. However, subtle features may not be well explained by electron-counting rules. In this work, we have discovered a unique example of ligand-controlled skeletal bonding in two recently reported gold nanoclusters with very similar compositions and geometries. We have shown that the superatomic orbitals of the common kernel of the two clusters undergo different ligand-field splitting because of the different ligand-field strengths in the two clusters. Such a difference is clearly revealed by constructing the Jellium orbitals via an orbital alignment process, and a subsequent localization of the Jellium orbitals allows us to obtain localized bonding models. Finally, on the basis of localized bonding models, we predict the existence of a ligated gold cluster with a [Au₃₂]⁴⁺ kernel.

中文翻译：

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结金纳米簇中的超原子配体场分裂。

金纳米簇由于其电子和光学特性而具有吸引力。已经提出了许多理论模型来通过电子计数方法解释其电子结构。但是，电子计数规则可能无法很好地解释这些细微特征。在这项工作中，我们在两个最近报道的金纳米团簇中发现了一个配体控制的骨架键合的独特例子，该团簇具有非常相似的组成和几何形状。我们已经表明，由于两个簇中不同的配体场强度，两个簇的共同核的超原子轨道经历了不同的配体场分裂。通过轨道对准过程构造Jellium轨道可以清楚地看出这种差异，随后对Jellium轨道进行本地化，使我们可以获得本地化的结合模型。最后，在局部结合模型的基础上，我们预测了具有[Au₃₂ ] ⁴⁺内核。