The distortion of band shapes seen in infrared attenuated total reflection (IR-ATR) spectroscopy of strongly absorbing materials such as water, relative to transmission sampling, is shown here to be due to the anomalous dispersion (AD) of water. This distortion occurs in addition to the normal 1/upsilon dependence, and, contrary to previous reports, is shown to not be due to chemical changes of water at the interface between the optical element and bulk solution. IR-ATR spectra of water were modeled with approximation-free calculations. The modeled spectra are compared with experimental ATR spectra for different internal reflection elements, and the results are discussed in terms of the AD optical effect.
Mehmet Hancer, Roger P. Sperline, and Jan D. Miller, "Anomalous Dispersion Effects in the IR-ATR Spectroscopy of Water," Appl. Spectrosc. 54, 138-143 (2000)
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