From the evaluation of sample difference spectra based on Gaussian "model" peaks with known peak characteristics, it is shown that interpretation of some parameters from difference spectra, resulting from the ratioing or subtraction of a poor background spectra, may be inaccurate or misleading. Difference spectra of this type are commonly observed with the use of techniques such as subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), electrochemically modulated infrared reflectance spectroscopy (EMIRS), or similar infrared spectroelectrochemical techniques, as well as some microsample analyses, studies of biochemical processes, and infrared astronomical observations, to name just a few examples. A mathematical evaluation of the problem is offered to demonstrate what information may realistically be gained from the characteristics of difference spectra. It is shown that in the worst case, where frequency, intensity, and peak width are all changing due to some perturbation of the sample (e.g., from temperature, or surface potential changes between background and sample spectra, etc.), even a qualitative interpretation may not be possible. In many practical cases, however, we show that at least a qualitative interpretation of the data can be obtained from difference spectra. Spectroelectrochemical applications for the calculations shown here are presented as examples, although these results impact a wider range of applications.
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