An attenuated total reflectance far-UV spectrometer

An ultraviolet spectrometer based on attenuated total reflection (ATR) has been developed and tested for liquid water (light and heavy water) in the wavelength range from 140 to 300 nm, which includes the far ultraviolet (FUV) region. One of the principal limitations of FUV transmission spectra is the strong absorption of the solvent itself. High absorptivity of the n --> sigma(*) transition in water molecule has thus far prevented meaningful spectral measurements of aqueous solutions in the wavelength region under 170 nm. Our technique uses the evanescent wave created through total reflection when light is passed through an internal reflection element (IRE) in contact with the sample. Since the evanescent field is used as an optical path length, the method allows spectral measurements favorably comparable with that of transmittance method with a shorter path length than the wavelength of FUV light. In this study, we have designed an original miniature IRE probe made of sapphire that allows detection of the whole n --> sigma(*) transition absorption band of water down to 140 nm. The obtained ATR-FUV spectra closely match calculations based on the Fresnel formula. It is also confirmed that this spectrometer is equally effective for spectral measurements of nonaqueous solvents with significant absorptivities in the FUV region.