Superatomic Rydberg State Excitation

Abstract

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 both the high and low excited states of the gold superatoms and their SAMOs make a major contribution to electronic transitions. The radial distribution function (RDF) 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 two-dimensional ductility of planar superatoms’ transition orbitals, superatoms have the superiority in RSE regulation. Our findings provide a new source of superatom-based RSE and will contribute to the regulation and efficient preparation of Rydberg states.