Observation of mixed singlet-triplet Rb2 Rydberg molecules

We present high-resolution spectroscopy of Rb-2 ultralong-range Rydberg molecules bound by mixed singlet-triplet electron-neutral atom scattering. The mixing of the scattering channels is a consequence of the hyperfine interaction in the ground-state atom, as predicted recently by Anderson et al. [Phys. Rev. A 90, 062518 (2014)]. Our experimental data enable the determination of the effective zero-energy singlet s-wave scattering length for Rb. We show that an external magnetic field can tune the contributions of the singlet and the triplet scattering channels and therefore the binding energies of the observed molecules. This mixing of molecular states via the magnetic field results in observed shifts of the molecular line which differ from the Zeeman shift of the asymptotic atomic states. Finally, we calculate molecular potentials using a full diagonalization approach including the p-wave contribution and all orders in the relative momentum k, and compare the obtained molecular binding energies to the experimental data.