Two-Photon Pathway to Ultracold Ground State Molecules of ²³Na⁴⁰K

We report on high-resolution spectroscopy of ultracold fermionic \nak~Feshbach molecules, and identify a two-photon pathway to the rovibrational singlet ground state via a resonantly mixed \Bcres intermediate state. Photoassociation in a $^{23}$Na-$^{40}$K atomic mixture and one-photon spectroscopy on \nak~Feshbach molecules reveal about 20 vibrational levels of the electronically excited \ctrip state. Two of these levels are found to be strongly perturbed by nearby \Bsing states via spin-orbit coupling, resulting in additional lines of dominant singlet character in the perturbed complex {${\rm B}^1\Pi |v{=}4\rangle {\sim} {\rm c}^3\Sigma^+ | v{=}25\rangle$}, or of resonantly mixed character in {${\rm B}^1\Pi | v{=}12 \rangle {\sim}{\rm c}^3\Sigma^+ | v{=}35 \rangle$}. The dominantly singlet level is used to locate the absolute rovibrational singlet ground state ${\rm X}^1\Sigma^+ | v{=}0, J{=}0 \rangle$ via Autler-Townes spectroscopy. We demonstrate coherent two-photon coupling via dark state spectroscopy between the predominantly triplet Feshbach molecular state and the singlet ground state. Its binding energy is measured to be 5212.0447(1) \cm, a thousand-fold improvement in accuracy compared to previous determinations. In their absolute singlet ground state, \nak~molecules are chemically stable under binary collisions and possess a large electric dipole moment of $2.72$ Debye. Our work thus paves the way towards the creation of strongly dipolar Fermi gases of NaK molecules.