Rotational pattern difference in resolved fluorescence spectra with different detection schemes

The relative intensities of rotational lines in resolved fluorescence spect ra are dependent on the detection direction and the choice of the detection scheme when a grating monochromator is used. These differences arise from the spatially anisotropic distribution of the fluorescence, the rotational branch dependence of the fluorescence polarization, and the polarization de pendence of the monochromator grating efficiency. Both the anisotropy of th e emission and the rotational branch dependence of the fluorescence polariz ation are enhanced in double-resonance excitation schemes. In the present w ork, we analyze the relative intensities in the Li-7(2) 1(3)Sigma(g)(-) --> 1(b)(3)Pi(u) and 1(3)Delta(g) --> 1(b)(3)Pi(u) resolved fluorescence spect ra, observed following double-resonance excitation, for three different det ection schemes. (C) 1999 Academic Press.