Modeling thin layers of analytes on substrates for spectral analysis: use of solid/liquid n and k values to model reflectance spectra

Since solids are only sometimes seen <em>en masse</em> in a pure bulk form, and for liquids other than water almost never, a capability to model reflectance spectra from analytes deposited on various substrates would be highly advantageous. If available, the real, <em>n</em> ( ν ) , and imaginary, <em>k</em> ( ν ) , components of the complex refractive index, <em>n</em~ = <em>n</em> + <em>i</em><em>k</em>, can be used to simulate infrared spectra, accounting for reflection, refraction, and absorption phenomena as a function of wavelength. We focus on using the Pacific Northwest National Laboratory (PNNL) derived <em>n</em> / <em>k</em> vectors for solid and liquid analytes deposited as thin layers on different types of substrates including conductors, such as aluminum, and inorganic dielectrics, such as glass. The model is an adaptation of the Monte Carlo ray trace modeling program, TracePro, extended through the use of its macrolanguage. The model is tested using thin films of organic liquids including silicone oil and no. 2 diesel fuel, as well as organic solids such as caffeine and acetaminophen on aluminum and glass. The predicted spectra for the solid films were compared to experimental hemispherical reflectance data measured using a Fourier transform spectrometer with an integrating sphere. The thickness of the calculated layer is a parameter for predicting the (transflectance) spectra and is obtained using the areal density measured from gravimetric methods to generate the thin-layer samples. Comparison of the calculated spectra with experimental hemispherical reflectance data shows excellent agreement, indicating promise for the use of measured <em>n</em> / <em>k</em> data to synthesize reference spectral data. In particular, accounting for the inhomogeneity of the deposits greatly improved the match with experimental data. Finally, the theoretical modeling shows that for thicker layers (ca. 20 to 100 μm) of typical organics possessing moderately strong <em>k</em> values, the longwave infrared features are often saturated and better spectral contrast is obtained from the overtone/combination bands in the shortwave infrared.