Measurement of the infrared optical constants for spectral modeling: n and k values for (NH4)2SO4 via single-angle reflectance and ellipsometric methods

The complex index of refraction, ñ = n + ik, has two components, n(ν) and k(ν), both a function of frequency, ν. The constant n is the real component, and k is the complex component, proportional to the absorption. In combination with other parameters, n and k can be used to model infrared spectra. However, obtaining reliable n/k values for solid materials is often difficult. In the past, the best results for n and k have been obtained from bulk, polished homogeneous materials free of defects; i.e. materials where the Fresnel equations are valid and there is no appreciable light scattering. Since it is often not possible to obtain such pure macroscopic samples, the alternative is to press the powder form of the material into a uniform disk. Recently, we have pressed such pellets from ammonium sulfate powder, and have measured the pellets’ n and k values via two independent methods: 1) ellipsometry, which measures the changes in amplitude and phase of light reflected from the material of interest as a function of wavelength and angle of incidence, and 2) single-angle reflectance using a specular reflectance device within a Fourier transform infrared spectrometer. This technique measures the change in amplitude of light reflected from the material of interest as a function of wavelength over a wide spectral domain. The optical constants are determined from the single-angle measurements using the Kramers-Kronig relationship, whereas an oscillator model is used to analyze the ellipsometric measurements. The n(ν) and k(ν) values determined by the two methods were compared to previous values determined from single crystal samples from which transmittance and reflectance measurements were made and converted to n(ν) and k(ν) using a simple dispersion model. [Toon et al., Journal of Geophysical Research, 81, 5733–5748, (1976)]. Comparison with the literature values shows good agreement, indicating that these are promising techniques to measure the optical constants of other materials.

[1]  Jeffrey Edward Moersch,et al.  Thermal emission from particulate surfaces : a comparison of scattering models with measured spectra , 1995 .

[2]  Timothy J. Johnson,et al.  Mid-infrared versus far-infrared (THz) relative intensities of room-temperature Bacillus spores , 2005 .

[3]  D. Griffiths Introduction to Electrodynamics , 2017 .

[4]  H. Fujiwara,et al.  Spectroscopic Ellipsometry: Principles and Applications , 2007 .

[5]  G. Hunt SPECTRAL SIGNATURES OF PARTICULATE MINERALS IN THE VISIBLE AND NEAR INFRARED , 1977 .

[6]  Hong Qi,et al.  Simultaneous retrieval of the complex refractive index and particle size distribution. , 2015, Optics express.

[7]  Bruce Hapke,et al.  Applications of an Energy Transfer Model to Three Problems in Planetary Regoliths: The Solid-State Greenhouse, Thermal Beaming, and Emittance Spectra , 1996 .

[8]  Yin-Fong Su,et al.  Quantitative reflectance spectra of solid powders as a function of particle size. , 2015, Applied optics.

[9]  C. Pantano,et al.  Infrared reflectance spectroscopy of porous silicas , 1993 .

[10]  Toya N. Beiswenger,et al.  Synthesis, electronic transport and optical properties of Si:α-Fe2O3 single crystals , 2016 .

[11]  Larry D. Travis,et al.  Light scattering by nonspherical particles : theory, measurements, and applications , 1998 .

[12]  Timothy J. Johnson,et al.  The quantitative infrared and NIR spectrum of CH 2 I 2 vapor: vibrational assignments and potential for atmospheric monitoring , 2006 .

[13]  F. Volz Infrared specular reflectance of pressed crystal powders and mixtures. , 1983, Applied optics.

[14]  B. Hapke Bidirectional reflectance spectroscopy: 1. Theory , 1981 .

[15]  J. H. Weaver,et al.  Optical constants of Cu, Ag, and Au revisited , 2015 .

[16]  D. Aspnes,et al.  Investigation of effective-medium models of microscopic surface roughness by spectroscopic ellipsometry , 1979 .

[17]  C E Lund Myhre,et al.  Optical constants of HNO3/H2O and H2SO4/HNO3/H2O at low temperatures in the infrared region. , 2005, The journal of physical chemistry. A.

[18]  M. Schubert,et al.  Variable-wavelength frequency-domain terahertz ellipsometry. , 2010, The Review of scientific instruments.

[19]  J. Rumble CRC Handbook of Chemistry and Physics , 2019 .

[20]  Barbara L. Walden,et al.  Measurement of Infrared Spectra of Dense Ceramics by Specular Reflectance Spectroscopy , 1990 .

[21]  Carolyn S. Brauer,et al.  Quantitative vapor-phase IR intensities and DFT computations to predict absolute IR spectra based on molecular structure: I. Alkanes , 2013 .

[22]  D. Aspnes Optical properties of thin films , 1982 .

[23]  Melissa D. Lane,et al.  Midinfrared optical constants of calcite and their relationship to particle size effects in thermal emission spectra of granular calcite , 1999 .

[24]  Owen B. Toon,et al.  The optical constants of several atmospheric aerosol species: Ammonium sulfate, aluminum oxide, and sodium chloride , 1976 .

[25]  Tanya L. Myers,et al.  Complex refractive index measurements for BaF 2 and CaF 2 via single-angle infrared reflectance spectroscopy , 2017 .

[26]  W. Spitzer,et al.  INFRARED PROPERTIES OF CaF$sub 2$, SrF$sub 2$, AND BaF$sub 2$ , 1962 .