A new model for the calculation of homogeneously broadened Raman spectral bandwidths and bandshapes

Abstract Raman spectral bandwidths and bandshapes can provide detailed information on the physics and chemistry of a sample. The Raman band reported by a spectrometer (observed Raman band [ORB]) is a result of contributions from the true, intrinsic Raman band (IRB) and the spectrometer slit function. To obtain the IRB spectral width and shape, the effects of the spectrometer slit function must be removed from the ORB by measuring the spectrometer slit function and modeling the ORB as a convolution of the IRB and slit function. Though this model has proven to be useful, it is not based on physical parameters of the measurement and is limited. Thus, new ways to model Raman bandshape and bandwidth are needed. I previously developed a new method of modeling Raman bands using spectrometer geometric optics to examine the dependence of Raman band intensity on slit width. The model calculates the intensity of the ORB from the contributions of a continuum of dispersed slit functions. Here, I extend the use of this model for examining ORB spectral widths and shapes. I show that the model produces the same result as the convolution model when using Lorentzian Raman and Gaussian slit functions, confirming the validity of the model. However, in contrast to the convolution model, the new model is based on spectrometer geometric optics allowing one to account for various optical effects when modeling Raman spectra. This is demonstrated by modeling the effects of slit width on the Raman spectrum. I use the model to provide a detailed, physical understanding of the effects of slit width and IRB width on Raman bandshapes.