Jiang De-en, Dai Sheng
Chemical Sciences Division and Center for Nanophase Materials Science, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
Inorg Chem. 2009 Apr 6;48(7):2720-2. doi: 10.1021/ic8024588.
Au(25)(SR)(18)(-) belongs to a new type of superatom that features an icosahedral Au(13) core-shell structure and a protective layer of six RS(Au-SR)(2) motifs. This superatom has a magic number of 8 free electrons that fully fill the 1s and 1p levels of the electron-shell model. By applying this superatom concept to the core-substitution chemistry of Au(25)(SR)(18)(-), we first scanned the periodic table for the potential core atom M by applying a simple rule derived from the 8-electron count and then optimized the selected candidates by density functional theory calculations to create many series of M@Au(24)(SR)(18)(q) core-shell nanoclusters. We found that 16 elements from groups 1, 2, and 10-14 of the periodic table can maintain both electronic and geometric structures of the original Au(25)(SR)(18)(-) magic cluster, indicating that the electron-counting rule based on the superatom concept is powerful in predicting viable M@Au(24)(SR)(18)(q) clusters. Our work opens up a promising area for experimental exploration.
Au(25)(SR)(18)(-)属于一种新型超原子，其具有二十面体Au(13)核壳结构以及由六个RS(Au-SR)(2)基序组成的保护层。该超原子具有8个自由电子的幻数，这些电子完全填满了电子壳层模型的1s和1p能级。通过将这种超原子概念应用于Au(25)(SR)(18)(-)的核取代化学，我们首先根据从8电子计数得出的简单规则在元素周期表中扫描潜在的核心原子M，然后通过密度泛函理论计算对选定的候选原子进行优化，以创建许多系列的M@Au(24)(SR)(18)(q)核壳纳米团簇。我们发现，元素周期表第1、2、10 - 14族中的16种元素能够保持原始Au(25)(SR)(18)(-)幻簇的电子和几何结构，这表明基于超原子概念的电子计数规则在预测可行的M@Au(24)(SR)(18)(q)团簇方面具有强大作用。我们的工作为实验探索开辟了一个有前景的领域。
