Orientational order determination by internal reflection infrared spectroscopy

PATIR-FTIR spectroscopy is a powerful technique for the determination of molecular order in thin films such as supported lipid membranes, but it relies on electromagnetic theory which is incomplete and potentially misleading. A complete derivation of the current theory for two, three and four phase systems has been presented. The two phase and thin film approximations most commonly used in practice have been shown to represent the thickness-dependent expressions from which they are derived with a high degree of accuracy. However, these expressions are based on the macroscopic behavior of dielectric materials, and may not be accurate when applied to microscopic circumstances. The potential error introduced is qualitatively and quantitatively significant. Further experimental and theoretical work is needed to verify the accuracy of this theory, or to refute and refine it. This effort to do this is warranted by the power and increasing popularity of the technique.