Subpicosecond Dynamics of Rydberg Excitons Produced from Ultraviolet Excitation of Neutral Cuprite (Cu₂O)_<i>n</i> Clusters, <i>n</i> &lt; 13

The ultrafast dynamics of subnanometer neutral cuprite clusters (Cu₂O)_<i>n</i>, <i>n</i> < 13, are examined with pump probe spectroscopy. Upon absorption of an ultraviolet (400 nm) photon, all clusters exhibit a subpicosecond lifetime that we attribute to carrier recombination. Density functional theory (DFT) shows a change in the structural motif between small planar clusters and three-dimensional structures at <i>n</i> = 4. This transition is accompanied by a change in the excited state relaxation behavior, marking the onset for which lifetimes increase gradually with size. Time-dependent DFT calculations show that the excited state lifetimes align with calculated topological parameters and charge carrier delocalization associated with the formation of Rydberg excitons. Terminal Cu atoms are found to be important for the production of Rydberg excitons at the lowest optically allowed excited state. Upon excitation, the electron resides on terminal Cu atoms and the hole becomes delocalized across the remainder of the cluster.