Impurity Electron Localization in Early-Transition-Metal-Doped Gold Clusters
Impurity Electron Localization in Early-Transition-Metal-Doped Gold Clusters
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DOI：
10.1021/jp511927q
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发表时间：
2015-02
影响因子：
3.7
通讯作者：
K. Hirsch;V. Zamudio-Bayer;A. Langenberg;M. Vogel;J. Rittmann;S. Forin;T. Möller;B. Issendorff;J. T. Lau
中科院分区：
文献类型：
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作者：
K. Hirsch;V. Zamudio-Bayer;A. Langenberg;M. Vogel;J. Rittmann;S. Forin;T. Möller;B. Issendorff;J. T. Lau
我们对尺寸范围在\(n = 1 - 9\)的尺寸选择的、自由的、阳离子的、过渡金属掺杂（\(Sc\)、\(Ti\)、\(V\)、\(Cr\)）金团簇进行了\(X\)射线吸收光谱研究。通过在电荷转移多重态框架内对\(X\)射线吸收光谱进行建模，确定了杂质原子的电子构型，这使得能够量化杂质\(3d\)态的局域化程度。根据掺杂元素和主体团簇尺寸的不同，我们发现局部电子结构的行为存在很大差异。\(ScAu_{n}^{+}\)团簇显示出钪\(3d\)态与主体电子态的强烈杂化，但\(ScAu_{1}^{+}\)除外，在\(ScAu_{1}^{+}\)中我们发现一个完全局域化的\(3d\)电子。在\(TiAu_{n}^{+}\)团簇中，杂质原子的局部电子结构存在明显的奇偶交替。钛掺杂剂的\(3d\)占据数在奇数和偶数团簇中分别约为\(2\)和\(1.6\)个电子。在\(CrAu_{n}^{+}\)团簇中，掺杂剂的电子结构受……
We have performed X-ray absorption spectroscopy of size-selected, free, cationic, transition-metal-doped (Sc, Ti, V, Cr) gold clusters in a size range n = 1–9. The electronic configuration of the impurity atom was determined by modeling the X-ray absorption spectrum in a charge-transfer multiplet framework which makes it possible to quantify the amount of localization of the impurity 3d states. Depending on the dopant element and the host cluster size we find a wide variety in the behavior of local electronic structures. ScAun+ clusters show strong hybridization of the scandium 3d states with the host electronic states except for ScAu1+ where we find a completely localized 3d electron. In TiAun+ clusters a pronounced odd–even alternation is present in the local electronic structure of the impurity atom. The 3d occupation number of the titanium dopant is approximately 2 and 1.6 electrons in odd and even-numbered clusters, respectively. In CrAun+ clusters the electronic structure of the dopant is governed b...