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Infrared multiple‐angle incidence resolution spectrometry (IR‐MAIRS) is a recently developed spectroscopic technique that combines oblique incidence transmission measurements and chemometrics (multivariate analysis) to obtain both pure in‐plane (IP) and out‐of‐plane (OP) vibration spectra for a thin sample. IR‐MAIRS is established for analyzing the molecular orientation of organic thin films at atmospheric pressure, but it should also be powerful for the structural characterization of vapor‐deposited thin samples prepared in a vacuum. The application of IR‐MAIRS to vapor‐deposited amorphous water is particularly interesting in the fields of physical and interstellar chemistry, because it is a representative model material for interstellar icy dust grains. We recently developed an experimental setup for in situ IR‐MAIRS under low‐temperature, ultrahigh‐vacuum conditions, which thus facilitates measurements of interstellar ice analogs such as vapor‐deposited amorphous water. This review considers the theoretical framework of IR‐MAIRS and our recent experimental results for vapor‐deposited amorphous water. We present spectroscopic signatures for the perpendicular orientation of dangling‐OH bonds for three‐coordinated water molecules at the surface of amorphous water at 90 K. The absolute absorption cross section of the three‐coordinated dangling‐OH bonds is quantitatively measured as 1.0 ± 0.2 × 10 −18  cm 2  at 3696 cm −1 . As IR‐MAIRS can essentially be conducted using only a Fourier‐transform IR spectrometer and an angle‐controllable linear polarizer, it is a useful, low‐cost, and simple spectroscopic technique for studying laboratory analogs of interstellar ices including vapor‐deposited amorphous water.

Infrared multiple‐angle incidence resolution spectrometry for vapor‐deposited amorphous water