New spectroscopic data, spin-orbit functions, and global analysis of data on the AΣu+1 and bΠu3 states of Na2

The lowest electronically excited states of Na2 are of interest as intermediaries in the excitation of higher states and in the development of methods for producing cold molecules. We have compiled previously obtained spectroscopic data on the AΣu+1 and bΠu3 states of Na2 from about 20 sources, both published and unpublished, together with new sub-Doppler linewidth measurements of about 15 000 A←X transitions using polarization spectroscopy. We also present new ab initio results for the diagonal and off-diagonal spin-orbit functions. The discrete variable representation is used in conjunction with Hund’s case a potentials plus spin-orbit effects to model data extending from v=0 to very close to the 3S2+3P1∕22 limit. Empirical estimates of the spin-orbit functions agree well with the ab initio functions for the accessible values of R. The potential function for the A state includes an exchange potential for S+P atoms, with a fitted coefficient somewhat larger than the predicted value. Observed and calculat...