Abstract

Raman spectra are usually corrected according to the highly nonlinear wavelength-dependent functions of the monochromator transmission and the photomultiplier cathode response. In the case of resonance in which the exciting frequency is almost or exactly identical to one of the eigen frequencies of the molecule, the absorption of the incident laser light and the reabsorption of the scattered light falsify the Raman intensities. One method for correcting Raman intensities is the application of difference Raman spectroscopy. Several authors corrected resonance Raman signal intensities with theoretically derived functions which required the knowledge of the exact pathlength of the laser and the scattered light through the sample cell. The functions were related to the spectral internal absorbance of the sample and did not consider sample cell specific light intensity attenuations. To avoid this and to exclude imperfections in the pathlength determination, we used experimentally derived correction functions. The Raman signal intensity <i>I</i>_s recorded at right angle to the incident beam is a function of the excitation light intensity <i>I</i>₀, the number <i>N</i> of the exposed molecules, the fourth power of the absolute scattering frequency ν_s, and the sum σ of the squared tensor elements due to linearly polarized light: <i>I</i>_s = σν_s⁴<i>NI</i>₀. (1)

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