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A critical analysis of the B 1Πu–X 1Σ+g band system of the Na2 molecule has been made. The body of data on which the present analysis is based is much more extensive than that used in any previous analysis. The data for the analysis were obtained by a laser-induced fluorescence technique in which many collisionally induced satellite fluorescence series were observed in addition to the directly excited series. We have found the coefficients in a Dunham expansion that replicates the frequencies of 12 591 lines that originate in 1297 different V′, J′ levels with an rms deviation between the observed and calculated frequencies of 0.011 cm−1. The frequencies of the lines that appear in the present analysis are poorly replicated by use of the Dunham coefficients found by earlier workers. The RKR potential curves, for both the B and X states and the Franck–Condon factors for transitions between the two states, have been found. In contrast to previous analyses the theoretical centrifugal distortion coefficients, calculated from the rotationless RKR potential, agree closely with those directly found in the present analysis. The dissociation energies have been found to be 5988 cm−1 for the X state and 3116 cm−1 for the B state. The maximum of the potential barrier of the B state lies about 474 cm−1 above the 2P3/2+2S1/2 levels to which the B state dissociates.
Kusch et al. (Wed,) studied this question.