Experimental Characterization of Singlet Scattering Channels in Long-Range Rydberg Molecules

We observe the formation of long-range Cs-2 Rydberg molecules consisting of a Rydberg and a ground-state atom by photoassociation spectroscopy in an ultracold Cs gas near 6s(1/2) (F = 3, 4) --> np(3/2) resonances (n = 26-34). The spectra reveal two types of molecular states recently predicted by D.A. Anderson, S.A. Miller, and G. Raithel [Phys. Rev. A 90, 062518 (2014)]: states bound purely by triplet s-wave scattering with binding energies ranging from 400 MHz at n = 26 to 80 MHz at n = 34, and states bound by mixed singlet-triplet s-wave scattering with smaller and F-dependent binding energies. The experimental observations are accounted for by an effective Hamiltonian including s-wave scattering pseudopotentials, the hyperfine interaction of the ground-state atom, and the spin-orbit interaction of the Rydberg atom. The analysis enables the characterization of the role of singlet scattering in the formation of long-range Rydberg molecules and the determination of an effective singlet s-wave scattering length for low-energy-electron-Cs collisions.