Joint analysis of the Cs2 a3Σu+ and 1g (3(3)Π1g) states

Abstract

Sets of experimental data on the Cs(2) a(3)Σ(u)(+) and 1(g) (3(3)Π(1g)) states, including the bound-bound and bound-free fluorescence spectra, are analyzed simultaneously to produce the potential energy curves of both states in the form of the Morse long range multiparameter function. The attractive branch of the a(3)Σ(u)(+) state potential is improved relative to the one reported in our earlier work [F. Xie, V. B. Sovkov, A. M. Lyyra, D. Li, S. Ingram, J. Bai, V. S. Ivanov, S. Magnier, and L. Li, J. Chem. Phys. 130, 051102 (2009)], in which the data on this state alone were analyzed. Besides, the new potential of this state also includes the repulsive branch in the range spanned by the bound-free fluorescence spectra. We have not found experimental evidence of the double minimum character of the 3(3)Π(1g) state potential, predicted by ab initio calculations, at least up to v = 8. This fact testifies that the upper state observed is better described by the Hund coupling case (c), in which the case (a) electronic basis states are intermixed by the strong spin-orbit interaction.