Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Institute of Physical Science and Information Technology and AnHui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui, 230601, P. R. China.
Small. 2021 Jul;17(27):e2005162. doi: 10.1002/smll.202005162. Epub 2021 Jan 28.
Silver nanoclusters (NCs) are of significant interest owing to their interesting structural, electronic, and catalytic properties. Among these NCs, Ag (SR) is particularly attractive due to its identical geometry as its Au counterpart, Au (SR) . Herein, the site-specific electronic properties of Ag (SR) and Au (SR) using X-ray spectroscopy experiments and quantum simulations are presented. To overcome the final state effect observed in X-ray photoelectron spectroscopy (XPS), a unique method is developed to reliably analyze the charge transfer behavior of the NCs. Density functional theory calculations are combined with XPS to provide more insight into the electronic properties of the NCs. The differences in the XPS valence bands of these two NCs are further compared and interpreted using the relativistic effect. The first derivative of the X-ray absorption near-edge structure (XANES) spectrum is further used as a tool to sensitively probe the bonding properties of Ag (SR) . By combining the experimental XANES data and their site-specific quantum simulations, the large impact of the staple motif on the bonding properties of the NC is demonstrated. These findings highlight the unique electronic properties of each atomic site in Ag (SR) ; the effective X-ray analysis techniques developed here can offer new opportunities for the site-specific study of other NCs.
银纳米团簇（NCs）因其有趣的结构、电子和催化特性而备受关注。在这些 NCs 中，Ag（SR）因其与 Au（SR）相同的几何形状而特别有吸引力。本文通过 X 射线光谱实验和量子模拟，研究了 Ag（SR）和 Au（SR）的特定位置电子特性。为了克服 X 射线光电子能谱（XPS）中观察到的终态效应，开发了一种独特的方法来可靠地分析 NC 的电荷转移行为。密度泛函理论计算与 XPS 相结合，为 NC 的电子特性提供了更深入的了解。利用相对论效应，进一步比较和解释了这两种 NC 的 XPS 价带的差异。X 射线吸收近边结构（XANES）谱的一阶导数进一步用作灵敏探测 Ag（SR）键合性质的工具。通过结合实验 XANES 数据和它们的特定位置量子模拟，证明了订书钉基序对 NC 键合性质的巨大影响。这些发现突出了 Ag（SR）中每个原子位置的独特电子特性；这里开发的有效 X 射线分析技术可为其他 NC 的特定位置研究提供新的机会。
