A general method for spectroscopic determination of the incidence angle and number of reflections in ATR devices is described. This technique extends the inherent advantages of ATR by simplifying general quantitative spectroscopic measurements. Effects of polarization, beam focusing, errors of alignment, indices of refraction, handling of the optical elements, and surface activity of internal standard are discussed. Measured ATR absorbances are fitted mathematically with the use of incidence angle as a parameter. A standardizing solution, molar absorptivities for that solution, and knowledge of the dimensions of the internal reflection optical element are required. Application of the method to a cylindrical internal reflection (CIR) device gives the averaged incidence angle in the CIR with greater accuracy than is otherwise obtainable. With the use of a side-focusing Fourier transform spectrophotometer, the average incidence angle in the Spectra-Tech, Inc. "Micro-cell" "CIRCLE" CIR was 49.68 degrees ± 0.78%, and the number of solution-sensing internal reflections was 7.52 ± 1.95%.
R. P. Sperline, S. Muralidharan, and H. Freiser, "New Quantitative Technique for Attenuated Total Reflection (ATR) Spectrophotometry; Calibration of the "CIRCLE" ATR Device in the Infrared," Appl. Spectrosc. 40, 1019-1022 (1986)