Photoassociation of long-range nD Rydberg molecules.

We observe long-range homonuclear diatomic nD Rydberg molecules photoassociated out of an ultracold gas of Rb87 atoms for 34≤n≤40. The measured ground-state binding energies of Rb87(nD+5S1/2) molecular states are larger than those of their Rb87(nS+5S1/2) counterparts, which shows the dependence of the molecular bond on the angular momentum of the Rydberg atom. We exhibit the transition of Rb87(nD+5S1/2) molecules from a molecular-binding-dominant regime at low n to a fine-structure-dominant regime at high n [akin to Hund's cases (a) and (c), respectively]. In the analysis, the fine structure of the nD Rydberg atom and the hyperfine structure of the 5S1/2 atom are included.