Orientation effects on nitric acid dihydrate films.

An investigation of orientation effects in films of nitric acid dihydrate (NAD) is presented, based on a systematic study of transmission and reflection-absorption infrared (RAIR) spectra of samples of varying thickness. The samples are prepared by vapor deposition on Ge (for transmission spectroscopy) and on Al substrates (for RAIR spectroscopy) at 175 K to produce crystalline alpha-NAD films. Transmission spectra were recorded at normal incidence, and RAIR spectra were recorded at a grazing angle of 75 degrees, with polarized radiation. The observed spectra are compared with predictions of a classical Fresnel model, to test the available optical indices of NAD, which are of great importance for the accurate interpretation of data from remote sensing measurements. Whereas the procedure yields satisfactory results for transmission and s-polarized RAIR spectra, it is found that the agreement is not acceptable for p-polarized RAIR spectra. An explanation is suggested in terms of a preferential alignment of the films, with the (10-1) crystallographic plane of the crystal situated parallel to the substrate. The infrared activity of a band at approximately 1170 cm(-1) is explained in terms of a preferential orientation of the crystal domains in the film.