New spectroscopic data, spin-orbit functions, and global analysis of data on the A(1)Sigma(+)(u) and b(3)Pi(u) states of Na-2

作者：Qi P^*; Bai J; Ahmed E; Lyyra A M; Kotochigova S; Ross A J; Effantin C; Zalicki P; Vigue J; Chawla G; Field R W; Whang T J; Stwalley W C; Knoeckel H; Tiemann E; Shang J; Li L; Bergeman T

来源：Journal of Chemical Physics, 2007, 127(4): 044301.

DOI：10.1063/1.2747595

The lowest electronically excited states of Na-2 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spectroscopic data on the A (1)Sigma(+)(u) and b (3)Pi(u) states of Na-2 from about 20 sources, both published and unpublished, together with new sub-Doppler linewidth measurements of about 15 000 A 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 3 S-2+3 P-2(1/2) 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 calculated term values are presented in an auxiliary (EPAPS) file as a database for future studies on Na-2.

• 出版日期2007-7-28
• 单位清华大学