Mid-infrared spectroscopy of hemispherical water droplets

As an important component of atmospheric aerosols, water is profoundly related with aerosol hygroscopicity and provides a medium for atmospheric heterogeneous reactions. The quantitative analysis of water content in aerosol droplets is instrumental to understanding atmospheric chemistry, as well as to addressing the related environmental issues, such as air pollution and climate change. Fourier transform infrared (FTIR) spectroscopy has been widely adopted to quantify the amount of water content in atmospheric aerosols, which is based on the absorbance of OH functional group in proportion to water content. However, in the OH stretching vibration band around 3400 cm^-1, spectral distortions may occur, making a quantitative analysis impossible. In addressing this issue, here we put forth a model to simulate the FTIR absorption of hemispherical water droplets, along with a quantitative description of the spectral distortion. Our model prediction was benchmarked with the microscopic-FTIR experiments conducted on sodium sulfate droplets, and good agreements between theoretical and experimental results were found. We observed that the absorbance spanning across the mid-wavenumber infrared region increases with water absorption coefficients; while such an increasing trend was not seen in the 3400 cm^-1 band. We speculate that the spectral saturated absorption is related to the absorption coefficient of water and the ratio of the projected area of droplets to the aperture area. In addition, the effects of droplet size and number density on the absorption spectra were investigated. The waveband range of the saturated absorption broadens with an increase in droplet radius. On the other hand, as the number density of water droplets increases, the absorption at 3400 cm^-1 is enhanced, and the characteristic peak of condensed water becomes increasingly sharper, asymptotic to the typical infrared spectra of water collected by the pressing method.