Liu Zheng, Wu Xiaochen, Zhu Yu, Wang Rui, Yu Famin, Wang Zhigang
Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012, China.
J Phys Chem Lett. 2021 Dec 16;12(49):11766-11771. doi: 10.1021/acs.jpclett.1c03520. Epub 2021 Dec 2.
Superatomic molecular orbitals (SAMOs) have symmetries (angular quantum numbers) similar to those of atoms, and thus, it is possible to realize Rydberg state excitations (RSEs) in superatomic molecules. In this Letter, the feasibility of superatomic Rydberg state excitation (SRSE) is explored using gold superatoms based on first-principles calculations. The results show that the SRSE exists in the high and low excited states of the gold superatoms and their SAMOs make a major contribution to electronic transitions. The radial distribution function of electronic density shows that the main distribution of electrons in the lowest unoccupied molecular orbitals and other unoccupied superatomic molecular orbitals is extremely far from the geometric center, and thus, they can be unambiguously identified as Rydberg orbitals. We found that due to the two-dimensional ductility of the planar SAMOs, superatoms are superior in the RSE regulation. Our findings may provide a new source of superatom-based RSE and will contribute to the regulation and efficient preparation of Rydberg states.
超原子分子轨道（SAMOs）具有与原子相似的对称性（角量子数），因此，在超原子分子中实现里德堡态激发（RSEs）是可能的。在本信函中，基于第一性原理计算，利用金超原子探索了超原子里德堡态激发（SRSE）的可行性。结果表明，SRSE存在于金超原子的高激发态和低激发态中，且它们的SAMOs对电子跃迁起主要作用。电子密度的径向分布函数表明，最低未占据分子轨道和其他未占据超原子分子轨道中的电子主要分布在离几何中心极远的位置，因此，它们可被明确识别为里德堡轨道。我们发现，由于平面SAMOs的二维延展性，超原子在RSE调控方面具有优势。我们的研究结果可能为基于超原子的RSE提供一种新来源，并将有助于里德堡态的调控和高效制备。
