Abstract
Single-mode cw dye laser excitation spectra of the (0, 0), (1, 1), and (2, 2) bands of the B 2Σ +- X 2Σ + system of CaCl have been observed and assigned. Some 300 independent photo-luminescence spectra have been used in making the rotational assignment and demonstrate the power of the technique of line-by-line analysis in unraveling complex spectra. Spectroscopic constants (cm −1) obtained from a weighted least squares fit of the data are given below. Numbers in parentheses refer to 95% confidence limits in the last digit. X 2 Σ + B 2 Σ + T e 0 16856.69(2) ω e 369.8(10) 366.8(10) ω ex e 1.13(20) 1.28(20) B e 0.15200(54) 0.15448(54) α e 0.00063(34) 0.00073(35) D e 1.027(16) × 10 −7 1.097(17) × 10 −7 γ e (spin-rotation) +0.003 −0.0630(16) The ground-state rotational constant is in excellent agreement with the previous value obtained from the analysis of the C 2Π r- X 2Σ +. The B-state spin-rotation interaction constant is consistent with the pure precession estimate of the interaction between the A 2Π r and B 2Σ + states, which, in the one electron approximation, both have the unpaired electron in a calcium 4 p orbital.
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