Super-Excimer: Anomalous Bonding in a Metastable Excited-State Dimer of Superatomic Dimers

A new type of excimer formation was reported, which stems from an unexpected discovery of a short-lived excited-state dimer of superatomic dimers. In theoretical investigation of the dimer formation, it was found that the physical adsorption states maintain the closed-shell properties of the dimeric units via van der Waals interaction, while the chemical adsorption excited state is a broken-symmetry (BS) state, having a higher energy of about 0.5 eV. Potential energy surface calculations indicate that the short-lived metastable chemical bonding state can transform into energetically lower physical adsorption states by crossing a shallow energy barrier and eventually disintegrate into two ground-state dimers. Since the basic unit is a superatomic cluster, the chemical adsorption state discovered may be called "super-excimer", which opens up a new avenue for the discovery of tailorable excimer materials.