Ito Shun, Koyasu Kiichirou, Tsukuda Tatsuya
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
Carbon to Metal Coating Institute, Queen's University, Kingston, Ontario, K7L 3N6, Canada.
Angew Chem Int Ed Engl. 2025 Jul 21;64(30):e202508151. doi: 10.1002/anie.202508151. Epub 2025 Jun 1.
The key structural factors underlying the spin-orbit (SO) splitting of the 1P orbitals in thiolate-protected Au superatoms were investigated using cryogenic anion photoelectron spectroscopy (PES) and two-component density functional theory (2c-DFT) calculations. PES revealed that the 1P orbitals of the Au and Au@Ag superatomic cores undergo splitting, whereas those of the Ag core do not. According to 2c-DFT calculations, the SO splitting of the 1P orbitals of the Au superatom stems from the symmetry-dictated coupling between the 6p orbitals of the central Au atom and the 1P orbitals formed by the surrounding icosahedral Au shell, both of which are split by SO effects.
利用低温阴离子光电子能谱（PES）和双组分密度泛函理论（2c-DFT）计算，研究了硫醇盐保护的金超原子中1P轨道自旋轨道（SO）分裂的关键结构因素。PES表明，金和金@银超原子核心的1P轨道发生分裂，而银核心的1P轨道不发生分裂。根据2c-DFT计算，金超原子1P轨道的SO分裂源于中心金原子的6p轨道与周围二十面体金壳形成的1P轨道之间由对称性决定的耦合，这两者都因SO效应而分裂。
