We report on photoassociation spectroscopy probing the potential of the bi-alkali NaCs molecule, identifying eleven vibrational lines between and of the excited potential, and resolving their rotational and hyperfine structure. The observed lines are assigned by fitting to an effective Hamiltonian model of the excited state structure with rotational and hyperfine constants as free parameters. We discuss unexpected broadening of select vibrational lines, and its possible link to strong spin-orbit coupling of the potential with the nearby and manifolds. Finally we report use of the line as an intermediate state for two-photon transfer of weakly bound Feshbach molecules to the rovibrational ground state of the manifold.

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