Spectroscopy , internal

B-75MI4I703 G. Salmona in Proceedings of the 18th International Spectroscopy Colloquium, ... 

The third important source for infonnation on modem Raman spectroscopy are the books cataloguing the proceedings of the International Conference on Raman Spectroscopy (ICORS) [37]. ICORS is held every two years at various international locations and feahires hundreds of contributions from leading research groups covering all areas of Raman spectroscopy. Although the published presentations are quite limited in lengdi, they each contain references to the more substantial works and collectively provide an excellent overview of current trends m Raman spectroscopy. A snapshot or brief sununary of the 1998 conference appears at the end of this chapter. 

Laser Raman diagnostic teclmiques offer remote, nonintnisive, nonperturbing measurements with high spatial and temporal resolution [158], This is particularly advantageous in the area of combustion chemistry. Physical probes for temperature and concentration measurements can be debatable in many combustion systems, such as furnaces, internal combustors etc., since they may disturb the medium or, even worse, not withstand the hostile enviromnents [159]. Laser Raman techniques are employed since two of the dominant molecules associated with air-fed combustion are O2 and N2. Flomonuclear diatomic molecules unable to have a nuclear coordinate-dependent dipole moment caimot be diagnosed by infrared spectroscopy. Other combustion species include CFl, CO2, FI2O and FI2 [160]. These molecules are probed by Raman spectroscopy to detenuine the temperature profile and species concentration m various combustion processes. 

Coherent anti-Stokes Raman spectroscopy (CARS) [59] has also found utility in the detemiination of the internal state distributions of products of chemical reactions. This is one of several coherent Raman spectroscopies based on the... 

No molecule is completely rigid and fixed. Molecules vibrate, parts of a molecule may rotate internally, weak bonds break and re-fonn. Nuclear magnetic resonance spectroscopy (NMR) is particularly well suited to observe an important class of these motions and rearrangements. An example is tire restricted rotation about bonds, which can cause dramatic effects in the NMR spectrum (figure B2.4.1). 

Chromatographic Science European Spectroscopy News European Mass Spectrometry International Journal of Mass Spectrometry International Journal of Mass Spectrometry and Ion Processes (formerly Journal of Mass Spectrometry and Ion Physics)... 

Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. Attenuated total redectance (atr) ftir spectroscopy is based on the principle of total internal redection (40). Methods based on internal redection in the uv and visible regions of the spectmm are also common in addition to those in the ir region. The implementation of internal redection in the ir region of the spectmm provides a means of obtaining ir spectra of surfaces or interfaces, thus providing moleculady-specific vibrational information. 

Atr—ftir can be readily performed on most commercial ftir spectrometers through the use of an attachment for atr spectroscopy. These devices provide ir-transparent internal reflection elements that are typically made of Ge, KRS-5, ZnSe, or ZnS. These internal reflection elements are made of materials that are of extremely high purity to avoid losses from absorption by impurities in these devices. Coupling of a thin film or surface sample to one of these reflection elements is accompHshed by pressing the sample against the element while acquiring the spectmm. 

N. J. Harrick, Internal Reflection Spectroscopy, ]olm. Wiley Sons, Inc., New York, 1967. 

Finished zinc and zinc aHoys are usuaHy analyzed for metals other than zinc by emission spectroscopy and the zinc determined by difference. ASTM method E 27 describes a technique using a dissolved sample and photographic detection. The internal standard is the zinc line at 267.0 nm. However, procedures using soHd samples are generaHy preferred and photoelectric detection often replaces optical detection. Samples are cast and machined on the surface where the arc is stmck. Up to 15 elements can be determined in a few minutes by modem automatic spectrometers. ASTM gives wet chemical methods for metals other than zinc (79). 

In Figure 2 the bond lengths and internal bond angles are given for some of the simple azines. Gas-phase electron diffraction, microwave spectroscopy, or the two techniques in combination, provided the results on compounds which were sufficiently volatile but with insufficient tendency to crystallize at accessible temperatures X-ray diffraction provided the remainder. 

Internal surfaces were covered with a tan deposit layer up to 0.033 in. (0.084 cm) thick. The deposits were analyzed by energy-dispersive spectroscopy and were found to contain 24% calcium, 17% silicon, 16% zinc, 11% phosphorus, 7% magnesium, 2% each sodium, iron, and sulfur, 1% manganese, and 18% carbonate by weight. The porous corrosion product shown in Fig. 13.11B contained 93% copper, 3% zinc, 3% tin, and 1% iron. Traces of sulfur and aluminum were also found. Near external surfaces, up to 27% of the corrosion product was sulfur. 

Removal of deposits and corrosion products from internal surfaces revealed irregular metal loss. Additionally, surfaces in wasted areas showed patches of elemental copper (later confirmed by energy-dispersive spectroscopy) (Fig. 13.12). These denickelified areas were confined to regions showing metal loss. Microscopic analysis confirmed that dealloying, not just redeposition of copper onto the cupronickel from the acid bath used during deposit removal, had occurred. 

Normal mode analysis exists as one of the two main simulation techniques used to probe the large-scale internal dynamics of biological molecules. It has a direct connection to the experimental techniques of infrared and Raman spectroscopy, and the process of comparing these experimental results with the results of normal mode analysis continues. However, these experimental techniques are not yet able to access directly the lowest frequency modes of motion that are thought to relate to the functional motions in proteins or other large biological molecules. It is these modes, with frequencies of the order of 1 cm , that mainly concern this chapter. 

XAFS V, Proceeding of the Fifth International Conference on X-ray Absorption Fine Structure. (J. M. de Leon, E. A. Stern, D. E. Sayers, Y. Ma, and J. J. Rehr, eds.) North-Holland, Amsterdam, 1989. Also in Physica B. 158, 1989. Report of the International Workshop on Standards and Criteria in X-ray Absorption Spectroscopy (pp. 701-722) is essential reading. 

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