Infrared and Raman spectroscopie

Infrared and Raman spectroscopy each probe vibrational motion, but respond to a different manifestation of it. Infrared spectroscopy is sensitive to a change in the dipole moment as a function of the vibrational motion, whereas Raman spectroscopy probes the change in polarizability as the molecule undergoes vibrations. Resonance Raman spectroscopy also couples to excited electronic states, and can yield fiirtlier infomiation regarding the identity of the vibration. Raman and IR spectroscopy are often complementary, both in the type of systems tliat can be studied, as well as the infomiation obtained. 

Both infrared and Raman spectroscopy provide infonnation on the vibrational motion of molecules. The teclmiques employed differ, but the underlying molecular motion is the same. A qualitative description of IR and Raman spectroscopies is first presented. Then a slightly more rigorous development will be described. For both IR and Raman spectroscopy, the fiindamental interaction is between a dipole moment and an electromagnetic field. Ultimately, the two... 

Advances in Infrared and Raman Spectroscopy [36] provides review articles, both fiindamental and applied, in the fields... 

Lee D and Albrecht A C 1985 A unified view of Raman, resonance Raman, and fluorescence spectroscopy (and their analogues in two-photon absorption) Advances in Infrared and Raman Spectroscopy vo 12, ed R J H Clark and R E Hester (New York Wiley) pp 179-213... 

Bewiok A and Pons S 1985 Infrared speotrosoopy of the eleotrode-eleetrolyte solution interfaoe Advances in Infrared and Raman Spectroscopy ed R J FI Clark and R E Flester (New York Wiley Fleyden) 12 1-63... 

This book, originally published in 1950, is the first of a classic tliree-volume set on molecular spectroscopy. A rather complete discussion of diatomic electronic spectroscopy is presented. Volumes 11 (1945) and 111 (1967) discuss infrared and Raman spectroscopy and polyatomic electronic spectroscopy, respectively. 

The vibrational states of a molecule are observed experimentally via infrared and Raman spectroscopy. These techniques can help to determine molecular structure and environment. In order to gain such useful information, it is necessary to determine what vibrational motion corresponds to each peak in the spectrum. This assignment can be quite difficult due to the large number of closely spaced peaks possible even in fairly simple molecules. In order to aid in this assignment, many workers use computer simulations to calculate the vibrational frequencies of molecules. This chapter presents a brief description of the various computational techniques available. 

The section on Spectroscopy has been retained but with some revisions and expansion. The section includes ultraviolet-visible spectroscopy, fluorescence, infrared and Raman spectroscopy, and X-ray spectrometry. Detection limits are listed for the elements when using flame emission, flame atomic absorption, electrothermal atomic absorption, argon induction coupled plasma, and flame atomic fluorescence. Nuclear magnetic resonance embraces tables for the nuclear properties of the elements, proton chemical shifts and coupling constants, and similar material for carbon-13, boron-11, nitrogen-15, fluorine-19, silicon-19, and phosphoms-31. 

Equations (6.5) and (6.12) contain terms in x to the second and higher powers. If the expressions for the dipole moment /i and the polarizability a were linear in x, then /i and ot would be said to vary harmonically with x. The effect of higher terms is known as anharmonicity and, because this particular kind of anharmonicity is concerned with electrical properties of a molecule, it is referred to as electrical anharmonicity. One effect of it is to cause the vibrational selection mle Au = 1 in infrared and Raman spectroscopy to be modified to Au = 1, 2, 3,. However, since electrical anharmonicity is usually small, the effect is to make only a very small contribution to the intensities of Av = 2, 3,. .. transitions, which are known as vibrational overtones. 

Schrader, B. (1995) Infrared and Raman Spectroscopy, Wiley-VCH, Weinheim. 

A small but artistically interesting use of fluorspar is ia the productioa of vases, cups, and other ornamental objects popularly known as Blue John, after the Blue John Mine, Derbyshire, U.K. Optical quaUty fluorite, sometimes from natural crystals, but more often artificially grown, is important ia use as iafrared transmission wiadows and leases (70) and optical components of high energy laser systems (see Infrared and RAMAN spectroscopy Lasers) (71). 

Materials characterization techniques, ie, atomic and molecular identification and analysis, ate discussed ia articles the tides of which, for the most part, are descriptive of the analytical method. For example, both iaftared (it) and near iaftared analysis (nira) are described ia Infrared and raman SPECTROSCOPY. Nucleai magaetic resoaance (nmr) and electron spia resonance (esr) are discussed ia Magnetic spin resonance. Ultraviolet (uv) and visible (vis), absorption and emission, as well as Raman spectroscopy, circular dichroism (cd), etc are discussed ia Spectroscopy (see also Chemiluminescence Electho-analytical techniques It unoassay Mass specthot thy Microscopy Microwave technology Plasma technology and X-ray technology). 

Instrumental Interface. Gc/fdr instmmentation has developed around two different types of interfacing. The most common is the on-the-fly or flow cell interface in which gc effluent is dkected into a gold-coated cell or light pipe where the sample is subjected to infrared radiation (see Infrared and raman spectroscopy). Infrared transparent windows, usually made of potassium bromide, are fastened to the ends of the flow cell and the radiation is then dkected to a detector having a very fast response-time. In this light pipe type of interface, infrared spectra are generated by ratioing reference scans obtained when only carrier gas is in the cell to sample scans when a gc peak appears. 

Reaction with hydrogen is very slight below 800°C, but reduction occurs at higher temperatures. In addition to some SiO formation, the formation of SiOH and SiH groups has been demonstrated by infrared and Raman spectroscopy (96). 

B. Schrader, Infrared and Raman Spectroscopy Methods and Applications, VCH Pubhshers, New York, 1994. 

Infrared (ir) transmission depends on the vibrational characteristics of the atoms rather than the electrons (see Infrared and Raman spectroscopy). For a diatomic harmonic oscillator, the vibrational frequency is described by... 

Infrared (in) spectrometers are gaining popularity as detectors for gas chromatographic systems, particularly because the Fourier transform iafrared (ftir) spectrometer allows spectra of the eluting stream to be gathered quickly. Gc/k data are valuable alone and as an adjunct to gc/ms experiments. Gc/k is a definitive tool for identification of isomers (see Infrared and raman spectroscopy). 

Infrared Spectrophotometry. The isotope effect on the vibrational spectmm of D2O makes infrared spectrophotometry the method of choice for deuterium analysis. It is as rapid as mass spectrometry, does not suffer from memory effects, and requites less expensive laboratory equipment. Measurement at either the O—H fundamental vibration at 2.94 p.m (O—H) or 3.82 p.m (O—D) can be used. This method is equally appticable to low concentrations of D2O in H2O, or the reverse (86,87). Absorption in the near infrared can also be used (88,89) and this procedure is particularly useful (see Infrared and raman spectroscopy Spectroscopy). The D/H ratio in the nonexchangeable positions in organic compounds can be determined by a combination of exchange and spectrophotometric methods (90). 

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. 

This comprehensive review of theoretical models and techniques will be invaluable to theorists and experimentalists in the fields of infrared and Raman spectroscopy, nuclear magnetic resonance, electron spin resonance and flame thermometry. It will also be useful to graduate students of molecular dynamics and spectroscopy. 

It is well established that disulfur difluoride (S2F2) exists in two isomeric forms, the nonplanar disulfane FSSF and the branched thiosulfoxide form p2S=S, with the latter found to be the more stable isomer. Both isomers have been characterized by microwave spectroscopy, mass spectrometry, infrared and Raman spectroscopy as well as photoelectron spectra [6] (and refer-... 

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