Attenuated total reflectance

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Attenuated total reflection (ATR) is a sampling technique used in conjunction with infrared spectroscopy which enables samples to be examined directly in the solid or liquid state without further preparation.^[1]

ATR uses a property of

This evanescent effect only works if the crystal is made of an optical material with a higher refractive index than the sample being studied. Otherwise light is lost to the sample. In the case of a liquid sample, pouring a shallow amount over the surface of the crystal is sufficient. In the case of a solid sample, samples are firmly clamped to ensure good contact is made and to remove trapped air that would reduce signal intensity. The signal to noise ratio obtained depends on the number of reflections but also on the total length of the optical light path which dampens the intensity. Therefore, a general claim that more reflections give better sensitivity cannot be made.^{[citation needed]}

Typical materials for ATR crystals include germanium, KRS-5 and zinc selenide, while silicon is ideal for use in the Far-IR region of the electromagnetic spectrum. The excellent mechanical properties of diamond make it an ideal material for ATR, particularly when studying very hard solids, although the broad diamond phonon band between 2600 and 1900 cm⁻¹ significantly decreases signal to noise in this region. The shape of the crystal depends on the type of spectrometer and nature of the sample. With dispersive spectrometers, the crystal is a rectangular slab with chamfered edges, seen in cross-section in the illustrations. Other geometries use prisms, half-spheres, or thin sheets.^{[citation needed]}

Applications

Infrared (IR) spectroscopy by ATR is applicable to the same chemical or biological systems as the transmission method. One advantage of ATR-IR over transmission-IR is the limited path length into the sample. This avoids the problem of strong attenuation of the IR signal in highly absorbing media such as aqueous solutions. For ultraviolet or visible light (UV/Vis) the evanescent light path is sufficiently short such that interaction with the sample is decreased with wavelength. For optically dense samples, this may allow for measurements with UV. Also, as no light path has to be established single shaft probes are used for process monitoring and are applicable in both the near and mid infrared spectrum.^{[citation needed]}

Recently, ATR-IR has been applied to

• Surface plasmon resonance

Sources