Perturbation-facilitated all-optical triple resonance spectroscopy of the Na2 b 3Πu state

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Abstract
The Na2 b 3Π u state has been studied by the continuous wave (cw) all‐optical triple resonance (AOTR) technique. The AOTR technique used here corresponds to a perturbation‐facilitated optical–optical double resonance (PFOODR) excitation through A 1Σ u +∼b 3Π u mixed intermediate levels from the ground state to the 2 3Π g state and stimulated emission pumping (SEP) of the 2 3Π g →b 3Π u transition. This sub‐Doppler high‐resolution PFOODR‐SEP technique has allowed us to reach many b 3Π u levels (Ω=0, 1, 2, perturbed and unperturbed, including low v below the A 1Σ u + potential minimum and higher vibrational levels up to v=57). Based on these new high resolution data and previous results from high resolution spectroscopy, we have determined a new set of deperturbed molecular constants from the b 3Π u state up to v=57, the corresponding RKR potential energy curve and the A 1Σ u +∼b 3Π u spin–orbit interaction constants. This represents an example of a powerful and general technique for observing a ‘‘dark’’ (e.g., triplet) perturbing state when only the ‘‘bright’’ (e.g., singlet) perturbed state is well known from single photon spectroscopy.

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