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Polarization spectroscopy was applied to the rotational analysis of the 2B1 (K'=0)-2A1 (K″=1) subbands of NO2 at 495, 474, 455 and 474 nm. The lines of the Q branch were distinguished from the lines of the P and R branches by using a linearly or circularly polarized pump beam. The rotational lines were clearly assigned by using this method. Shifts of the energy levels and large spin splittings showing level crossings are seen in the obtained rotational structures. It is concluded from the analysis that the spin splittings in the 2B1 state is intrinsically very small and large splittings are due to perturbation by other vibronic states.

Rotational analysis of the 2B1 state of NO2 by polarization spectroscopy.