Shah Aaron, Banjade Huta, Long Zhen-Chao, Gao Zhao-Ou, Xu Hong-Guang, Zheng Weijun, Jena Puru
Physics Department, Virginia Commonwealth University, Richmond, Virginia 23284-2000, United States.
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
J Phys Chem Lett. 2022 Jun 2;13(21):4721-4728. doi: 10.1021/acs.jpclett.2c00910. Epub 2022 May 24.
Gold, although chemically inert in its bulk state, is reactive at the nanoscale and, in small clusters, even behaves like a hydrogen atom. Using a photoelectron spectroscopy experiment and first-principles theory, we show that Au also behaves like a halogen in small clusters. This is evident not only in strong resemblance between the photoelectron spectra of AuF and AuF but also in Au exhibiting one of the signature properties of halogens, its ability to form superhalogens with electron affinities higher than that of any halogen atom. For example, the electron affinity (EA) of AuF is 4.17 eV, while AuF, a known superhalogen, has an EA of 4.47 eV. Of particular interest is AuF, which, in spite of being a closed-shell system, is a pseudohalogen with an EA of 3.3 ± 0.1 eV. Here, one of the Au atoms behaves like a halogen, making AuF mimic the property of AuF.
金虽然在块状状态下化学性质不活泼，但在纳米尺度上具有反应性，并且在小团簇中甚至表现得像氢原子。通过光电子能谱实验和第一性原理理论，我们表明金在小团簇中也表现得像卤素。这不仅体现在AuF和AuF的光电子能谱之间的强烈相似性上，还体现在金展现出卤素的标志性特性之一，即它能够形成电子亲和能高于任何卤素原子的超卤素。例如，AuF的电子亲和能（EA）为4.17电子伏特，而已知的超卤素AuF的电子亲和能为4.47电子伏特。特别令人感兴趣的是AuF，尽管它是一个闭壳层系统，但却是一种伪卤素，电子亲和能为3.3±0.1电子伏特。在这里，其中一个金原子表现得像卤素，使得AuF模仿了AuF的性质。
