Abstract

The 3(3 d) 3Σ g + state of the Na 2 molecule has been observed for the first time by perturbation-facilitated optical-optical double-resonance (PFOODR) excitation spectroscopy through A 1Σ u + ∼ b 3Π u mixed intermediate levels. The rotational structure and the fine-hyperfine splittings of the 3 3Σ g + ← b 3Π u transitions are similar to the 4 3Σ g + ← b 3Π u transitions of Na 2. Absolute vibrational numbering of the 3 3Σ g + state was determined by comparing the experimental excitation intensities with the calculated Franck-Condon factors. Molecular constants and the RKR potential curve are also reported. A comparison of the molecular constants of all eight observed states dissociating to the same 3 s + 3 d asymptote with ab initio theory shows remarkably good agreement.

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