We report here ab initio calculated electronic transition dipole moments for the sodium dimer ion pair states of (1)Σg (+) symmetry. They vary strongly as a function of internuclear distance because of the effect of the Na(+) + Na(-) ion pair potential, which also causes the formation of additional wells and shoulders in the molecular potential energy curves. We also present a computational study of the transition dipole moment matrix elements and lifetimes for these ion-pair states.

Accurate knowledge of transition dipole moment matrix elements is crucial since important parameters associated with the interaction of light with matter, such as emission and absorption line intensities, lifetimes, and Einstein coefficients, depend on these matrix elements. We report here an experimental study of the Na 5Σ↔AΣ and 6Σ↔AΣ electronic transition dipole moments and their dependence on internuclear distance. We have measured absolute transition dipole matrix elements for ro-vibrational transitions of the Na 5Σ↔AΣ and 6Σ↔AΣ electronic transitions using Autler-Townes and optical-optical double resonance spectroscopy, and we compare the results to ab initio theoretical values [A. Sanli et al., J. Chem. Phys. 143, 104304 (2015)].

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