Superatomic Orbitals under Spin鈥揙rbit Coupling
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- 作者：De-en Jiang ; Michael K眉hn ; Qing Tang ; Florian Weigend
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2014
- 出版时间：October 2, 2014
- 年：2014
- 卷：5
- 期：19
- 页码：3286-3289
- 全文大小：285K
- ISSN：1948-7185
文摘
The Au25(SR)18鈥?/sup> cluster has been the poster child of success in applying the superatom complex concept and remains the most studied system of all of the monolayer-protected metal clusters. In this Letter, we try to solve a mystery about this cluster: the low-temperature UV鈥搗is absorption spectrum shows double peaks below 2.0 eV while simulation by scalar relativistic time-dependent density functional theory (TDDFT) shows only one peak in this region. Using a recently implemented two-component TDDFT, we show that spin鈥搊rbit coupling (SOC) leads to those two peaks by splitting the 1P superatomic HOMO orbitals. This work highlights the importance of SOC in understanding the electronic structure and optical absorption of thiolated gold nanoclusters, which has not been realized previously.