Rotational Pattern Difference in Resolved Fluorescence Spectra with Different Detection Schemes

• Published in: Journal of molecular spectroscopy Vol. 196; no. 2; pp. 197 - 211
• Main Authors: Chen, Hongmin, Li, Li, Lazarov, G., Wang, X., Lyyra, A.M., Huennekens, J., Field, R.W.
• Format: Journal Article
• Language: English
• Published: United States Elsevier Inc 01.08.1999
• Subjects: 7Li2-resolved fluorescence; fluorescence detection; polarization of fluorescence; spectral patterns of fluorescence; 7Li2-resolved fluorescence; polarization of fluorescence; spectral patterns of fluorescence; fluorescence detection
• ISSN: 0022-2852; 1096-083X
• DOI: 10.1006/jmsp.1999.7873

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 7Li2 13Σ−g → 1(b)3Πu and 13Δg → 1(b)3Πu resolved fluorescence spectra, observed following double-resonance excitation, for three different detection schemes.