Infrared reflectance absorbance

Vibrational spectra were recorded using the polarization-modulated infrared reflection absorbance technique (PM-IRRAS). The spectrometer, the electrochemical cell, and the sample preparation and cleaning procedures are all described elsewhere (1 7) All of the measurements were performed using 0.5 M SO solutions, either with or without an added nitrile compound or SnCl,. The solutions were saturated with CO by bubbling the gas through their storage reservoirs before admitting them into the sample cell. 

The kinetics of the copolymerization of norbornenes and maleic anhydride has been analyzed in situ by IR spectroscopy [254]. Gas phase FT-IR has been combined with TGA to investigate outgassing from the ketal-based KRS-XE e-beam resist [222]. A flow cell which allows exposure and heating of a resist-coated wafer was attached to the IR spectrometer to study exposure- and temperature-dependent outgassing. Real time deprotection of the KRS resist has been also monitored by infrared reflectance-absorbance spectroscopy [222,494]. 

Recent work in our laboratory has shown that Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS) can be used routinely to measure vibrational spectra of a monolayer on a low area metal surface. To achieve sensitivity and resolution, a pseudo-double beam, polarization modulation technique was integrated into the FT-IR experiment. We have shown applicability of FT-IRRAS to spectral measurements of surface adsorbates in the presence of a surrounding infrared absorbing gas or liquid as well as measurements in the UHV. We now show progress toward situ measurement of thermal and hydration induced conformational changes of adsorbate structure. The design of the cell and some preliminary measurements will be discussed. 

Perhaps the first evidence for the breakdown of the Born-Oppenheimer approximation for adsorbates at metal surfaces arose from the study of infrared reflection-absorption line-widths of adsorbates on metals, a topic that has been reviewed by Hoffmann.17 In the simplest case, one considers the mechanism of vibrational relaxation operative for a diatomic molecule that has absorbed an infrared photon exciting it to its first vibrationally-excited state. Although the interpretation of spectral line-broadening experiments is always fraught with problems associated with distinguishing... 

NIR spectra are acquired using dried tissue, either whole or ground. The reflectance is measured relative to a so-called white reference, which is a highly reflective surface, such as Gore-Tex or white ceramic. Near-infrared reflectance spectra, or absorbance spectra, defined as log(l/R), with R being the reflectance, look rather flat. For analysis purposes the second derivative of the spectra is often used, because it enhances certain spectral features. 

Modern methods of vibrational analysis have shown themselves to be unexpectedly powerful tools to study two-dimensional monomolecular films at gas/liquid interfaces. In particular, current work with external reflection-absorbance infrared spectroscopy has been able to derive detailed conformational and orientational information concerning the nature of the monolayer film. The LE-LC first order phase transition as seen by IR involves a conformational gauche-trans isomerization of the hydrocarbon chains a second transition in the acyl chains is seen at low molecular areas that may be related to a solid-solid type hydrocarbon phase change. Orientations and tilt angles of the hydrocarbon chains are able to be calculated from the polarized external reflectance spectra. These calculations find that the lipid acyl chains are relatively unoriented (or possibly randomly oriented) at low-to-intermediate surface pressures, while the orientation at high surface pressures is similar to that of the solid (gel phase) bulk lipid. 

With infrared reflection absorption spectroscopy (IRRAS), it is possible to obtain information about the orientation of enzyme molecules adsorbed on flat metal surfaces (3,4). Electric dipole-transition moments oriented perpendicular to a flat metal surface show enhanced IR absorbance. IR bands due to vibrations of groups with transition moments oriented parallel to the surface are not observed. The IR-beam component which is polarized perpendicular to the plane of incidence (parallel to the surface) contains no information and can be eliminated by using a polarizer. 

Studies of carbonate-sulfonate RMs in engine oil on the antiwear performance of ZDDP, using reflectance-absorbance infrared spectroscopy RAIR, X-ray photoelectron spectroscopy XPS and Auger electron spectroscopy AES, showed that the tribofilms were inorganic amorphous phosphates, mainly orthophosphate (P043 ) and pyrophosphate (P2074 ) associated with zinc and magnesium (from the hard-core RMs) (Willermet et al., 1991 and 1992). 

XRF = X-ray fluorescence spectroscopy, XPS = X-ray photoelectron spectroscopy, AES = Auger electron spectroscopy, XANES = X-ray absorption near edge spectroscopy, RAIR = Reflectance-absorbance infrared spectroscopy, EXAFS = X-ray absorption fine-structure spectroscopy, ECR = Electric contact resistance, NMR = Nuclear magnetic resonance spectroscopy, IPS = Imaging photoelectron spectromicroscopy. 

Some of the techniques described in this chapter used most widely today are Auger electron spectroscopy, X-ray photoelectron spectroscopy, electron-probe micro-analysis, low energy electron diffraction, scanning electron microscope, ion scattering spectroscopy, and secondary ion mass spectroscopy. The solid surface, after liberation of electrons, can be analyzed directly by AES, XPS, ISS, and EPMA (nondestructive techniques), or by liberation of ions from surfaces using SIMS (involving the destruction of the surface). Apart from the surface techniques, reflectance-absorbance infrared (RAIR) spectroscopy has also been employed for film characterization (Lindsay et al., 1993 Yin et al., 1993). Some... 

Very thin films (monolayer or multilayer) can be studied by IR spectroscopy, provided that the IR beam crosses a reasonably large fraction of the monolayer this can be done by (i) grazing-angle techniques (whereby the IR beam angles of incidence and reflection are of the order of 1° to 3°) or (ii) multiple internal reflections of the IRbeam inside the monolayer (infrared reflectance and absorbance spectroscopy (IRRAS). Fig. 11.19 shows the chemical structure of an analyte (Fullerene-fcz s-[ethylthio-tetrakis(3,4-dibutyT2-thiophene-5-ethenyl)-5-bromo-3,4-dibutyl-2-thiophene] malonate),... 

In the first case, it has been recognized that if molecules are adsorbed on the surface of a metal, only part of the grazing incident radiation is reflected, part being absorbed by the adsorbed species. This absorption is greatly increased if the incident radiation is polarized perpendicular to the metal surface. This is the basis of so-called Infrared Reflection Absorption Spectroscopy (IRRAS) [27], which is applied widely to surface studies on metal surfaces. In these conditions, an additional selection rule applies ... 

Shaw and coworkers have studied the anodically induced formation of the a,7i complex [ CpFe(CO)2 2(p-ri ri -C=CPh)] from Cp(CO)2Fe-C=CPh by infrared reflectance spectroelectrochemistry (IRRAS). This process goes along with the cleavage of the Fe-alkynyl bond and attack of the CpFe(CO)2 electrophile thus formed onto the parent alkynyl complex. Such processes are commonly dubbed as mother-daughter (or father-son) reactions. The identity of the electrogenerated product was established by comparing its IR absorbances to those of the independently prepared product. 

Microwaves (0.3-300 GHz) lie between radiowave (RF) and infrared (IR) frequencies in the electromagnetic radiation spectrum. Microwaves can be reflected, absorbed and/or transmitted by materials. Microwaves can interact with materials through either polarization or conduction processes. Polarization involves the short-range displacement of charge through... 

Due to the absorption bands in NIR being weaker than in UV-Vis absorption, NIR spectrometry is not as useful for quantitative measurements but offers better qualitative analysis because of improved selectivity. NIR techniques can handle both liquid and solid samples. Near infrared reflectance analysis (NIRA) has found wide application in process analysis, especially for highly absorbing compounds such as foodstuffs Coal, grain, pulp and paper products and some pharmaceuticals can also be determined by NIRA ". The reflectance from the sample is reported relative to reflectance from a standard reference surface. 

B.K. Alsberg. W.G. Wade and R. Goodacre. Chemometric Analysis of Diffuse reflectance-absorbance Fourier Transform Infrared Spectra Using Rule Induction Methods Application to the Classification of Eubacterium Species, Applied Spectroscopy, 52(6) (1998), 823-832. 

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