Theory of infrared microspectroscopy for intact fibers

Infrared microspectroscopy is widely used for the chemical analysis of small samples. In particular, spectral properties of small cylindrical samples are important in forensic analysis, understanding relationships between microstructure and mechanical properties in fibers or fiber composites, and development of cosmetics and drugs for hair. The diameters of the constituent cylinders are typically of the order of the central wavelength of light used to probe the sample. Hence, structure and material spectral response are coupled and recorded spectra are usually distorted to the extent of becoming useless for molecular identification. In this paper, we apply rigorous optical theory to predict the spectral distortions observed in IR microspectroscopic data of fibers. The theory is used, first, to compute the changes that are observed for cylinders of various dimensions under different instrument configurations when compared to the bulk spectrum from the same material. We provide a method to recover intrinsic material spectral response from fibers by correcting for distortion introduced by the cylindrical structure. The theory reported here should enable the routine use of IR microspectroscopy and imaging for the molecular analysis of cylindrical domains in complex materials.