Rotational Pattern Difference in Resolved Fluorescence Spectra with Different Detection Schemes

The relative intensities of rotational lines in resolved fluorescence spectra 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 dependence of the monochromator grating efficiency. Both the anisotropy of the emission and the rotational branch dependence of the fluorescence polarization are enhanced in double-resonance excitation schemes. In the present work, we analyze the relative intensities in the (7)Li(2) 1(3)Sigma(-)(g) --> 1(b)(3)Pi(u) and 1(3)Delta(g) --> 1(b)(3)Pi(u) resolved fluorescence spectra, observed following double-resonance excitation, for three different detection schemes. Copyright 1999 Academic Press.