The Na23 3Πg state adiabatically dissociates to the 3s+4p atomic limit. The 3 3Πg levels below the 3s+3d atomic limit have been observed by perturbation facilitated optical–optical double resonance (PFOODR) fluorescence excitation spectroscopy. Energy levels above the 3s+3d atomic limit cannot be observed by detecting molecular fluorescence but are observable by detecting atomic 3d→3p fluorescence. The 3 3Πg state interacts with the 3s+3d2 3Πg state. At lower energy this interaction is responsible for many perturbations between bound vibrational levels of these two states. Above the 3s+3d limit, as a result of this interaction, the 3 3Πg state is strongly predissociated and the linewidths of levels close to the 3s+3d limit are about 22 cm−1. The predissociation interaction is due to an avoided crossing between the adiabatic 2 3Πg and 3 3Πg states at R≈2.85 Å. Weak predissociation of the 4 3Σg+ and 2 3Δg states are also observed and discussed.

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