Sampling for Raman Spectroscopy

Because Raman spectroscopy requires one only to guide a laser beam to the sample and extract a scattered beam, the technique is easily adaptable to measurements as a function of temperature and pressure. High temperatures can be achieved by using a small furnace built into the sample compartment. Low temperatures, easily to 78 K (liquid nitrogen) and with some diflSculty to 4.2 K (liquid helium), can be achieved with various commercially available cryostats. Chambers suitable for Raman spectroscopy to pressures of a few hundred MPa can be constructed using sapphire windows for the laser and scattered beams. However, Raman spectroscopy is the characterizadon tool of choice in diamond-anvil high-pressure cells, which produce pressures well in excess of 100 GPa. ... 

A small sample exploded violently upon laser irradiation for Raman spectroscopy. 

Sampling techniques for Raman spectroscopy are relatively general since the only requirement is that the monochromatic laser beam irradiate the sample of interest and the scattered radiation be focused upon the detector. 

Though the use of transmission geometry is common for many other spectroscopic techniques, it has not been widely nsed for Raman spectroscopy [39] In this case, illumination and collection optics are on opposite sides of the sample. The actual generation and travel of Raman photons through the sample is convoluted, but it is safe to conclude that the bulk of the sample is probed [40,41]. The large sample volume probed results in reduced subsampling errors. In one example, the use of the transmission mode enabled at least 25% reduction in prediction error compared to a small sampling area probe [42]. The approach is insensitive... 

Figure 2. Experimental set-up for Raman spectroscopy. The desired laser line is isolated from other plasma lines by a narrow bandpass filter or broadband prism monochromator, then focused onto a sample in a capillary tube. A collecting lens placed at a 90° angle to the incident beam focuses the scattered light onto the entrance slit of a monochromator with output to a photomultiplier tube (in the case of a scanning instrument) or a diode array detector.

Samples for analysis may be solids, liquids, or gases, or any forms in between and in combination, such as slurries, gels, and gas inclusions in solids. Samples can be clear or opaque, highly viscous or liquids with lots of suspended solids. While this variety is easy for Raman spectroscopy, it would be challenging for mid-IR and near-infrared (NIR) spectroscopy and numerous non-spectroscopic approaches. 

A small sample exploded violently upon laser irradiation for Raman spectroscopy. See other IRRADIATION DECOMPOSITION INCIDENTS, ORGANOMETALLICS... 

A limiting factor in noninvasive optical technology is variations in the optical properties of samples under investigation that result in spectral distortions44 8 and sampling volume (effective optical path length) variability 49-54 These variations will impact a noninvasive optical technique not only in interpretation of spectral features, but also in the construction and application of a multivariate calibration model if such variations are not accounted for. As a result, correction methods need to be developed and applied before further quantitative analysis. For Raman spectroscopy, relatively few correction methods appear in the literature, and most of them are not readily applicable to biological tissue.55-59... 

The same general principle that applies for intrinsic fluorescence should hold true for Raman spectroscopy as well. Unlike in fluorescence spectroscopy, spectral distortion owing to prominent absorbers is less of an issue in the NIR wavelength range. However, for quantitative analysis the turbidity-induced sampling volume variations become very significant and usually dominate over spectral distortions. 

Figure 3.4-1 Optical diagram of a commercial Michelson interferometer for infrared and Raman spectroscopy (Bruker IFS 66 with Raman module FRA 106). CE control electronics, D1/D2 IR detectors, BS beamsplitter, MS mirror scanner, IP input port, S IR source, AC aperture changer, XI — X3 external beams, A aperture for Raman spectroscopy, D detector for Raman spectroscopy, FM Rayleigh filter module, SC sample compartment with illumination optics, L Nd.YAG laser, SP sample position.

Thus, the optimum sample arrangement for Raman spectroscopy of crystal pow ders with a low absorption coefficient is a forward-scattering (0°) arrangement of coarse crystallites with an optimum thickness in a multiple scattering arrangement. These are the conditions for the investigation of colorless samples in the visible range of the spectrum. 

Figure 3.5-5 Sample arrangement for Raman spectroscopy. Optimal illumination of a a grating spectrometer in the 90° arrangement b of an interferometer in the 180° arrangement.

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