Molecular electronic spectroscopy by Fabry-Perot interferometry. Effect of nuclear quadrupole interactions on the line widths of the B3Πo+-X1Σg+ transition of the I2 molecule

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A pressure-scanning Fabry-Perot interferometer spectrometer was tested by recording the 5461 Å atomic lines of mercury in absorption in a radio-frequency discharge. The smallest half-width (full width at half height) measured was 0.024 cm-1. Assuming the indicated resolving power of 750 000, we studied the 18-0 and 20-1 vibrational bands near 5650 Å and the 30-0 band near 5350 Å in the B3Π0+-X1Σg+ transition of iodine vapor at a pressure of about 10 μ. Instead of lines sharper than those of mercury, lines at least 25% broader were found. Moreover, the half-width alternates with the rotational quantum number J, being about 0.030 cm-1 for even J'' and 0.035 cm-1 for odd J''. These widths are explained in detail by a nuclear electric quadrupole interaction in both states, with a difference in coupling constants of eQq' - eQq'' = 0.070 cm-1. The result is confirmed by our studies of 129I2 line widths and agrees well with a recent interpretation of saturated absorption by one rotational line in the 11-5 band of the same transition.

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