External reflection infrared spectroscopy

In addition to describing the conformation of the hydrocarbon chains for amphiphilic molecules at the A/W interface, external reflectance infrared spectroscopy is also capable of describing the orientation of the acyl chains in these monolayers as a function of the monolayer surface pressure. The analysis of the orientation distribution for an infrared dipole moment at the A/W interface proceeds based on classical electromagnetic theory of stratified layers (2). In particular, when parallel polarized radiation interacts with the A/W interface, the resultant standing electric field has contributions from both the z component of the p-polarized radiation normal to the interface, as well as the x component of the p-polarized radiation in the plane of the interface. The E field distribution for these two... 

In-Situ External Reflectance Infrared Spectroscopy in Electrochemistry. 136... 

Hoffmann H, Mayer U and Krischanitz A 1995 Structure of alkylsiloxane monolayers on silicon surfaces investigated by external reflection infrared spectroscopy Langmuir1304—12... 

Boston, Ma., March 1999, p.627-8. 012 ELUCIDATION OF CRYSTALLINE STRUCTURE IN POLYETHYLENE TEREPHTHALATE BY EXTERNAL REFLECTION INFRARED SPECTROSCOPY Cole K C Ajji A Pellerin E Canada,National Research Council (ACS,Div.of Polymer Chemistry)... 

Table 1 Optimum incidence angles and relative signal-to-noise ratios (SNR) for external reflection infrared spectroscopy with different substrate materials using p-polariazed light...

Brunner H, Mayer U, and Hoffmann H (1997) External reflection infrared spectroscopy of anisotropic adsorbate layers on dielectric substrates. Applied Spectroscopy 51 209-217. 

A second example involves reflectance infrared spectroscopic structural analysis of polydimethylsiloxane at the air-water interface. Surface pressure versus surface area or surface concentration isotherms of polydimethylsiloxane on water have been studied since 1947 at least (223). Upon compression, the isotherm begins at zero surface pressure at surface concentrations significantly below 0.75 mg/m. Around f 1 0.75 mg/m, the surface pressure tt jumps substantially to about 9 mN/m, where it exhibits a plateau until about T2 1.6 mg/m, where a small Tt jump occurs followed by a smaller rise (Fig. 31). Structural features associated with the various transitions have often been debated. Particular controversy is associated with the ix plateau aroimd 9 mN/m between Fi and T2 (224,225). In conjimction with other techniques, such as epifluorescence microscopy, external reflectance infrared spectroscopy was used to study microstructural features (coexistence of two phases) of polydimethylsiloxane CH3—[Si(CH3)2—Oln—SKCHala, spread at the air-water interface in the vicinity of the n plateau at 9 mN/m (226). A broad band containing several components is foimd in the 1000-1100 cm ... 

Polyimide surface modification by a wet chemical process is described. Poly(pyromellitic dianhydride-oxydianiline) (PMDA-ODA) and poly(bisphenyl dianhydride-para-phenylenediamine) (BPDA-PDA) polyimide film surfaces are initially modified with KOH aqueous solution. These modified surfaces are further treated with aqueous HC1 solution to protonate the ionic molecules. Modified surfaces are identified with X-ray photoelectron spectroscopy (XPS), external reflectance infrared (ER IR) spectroscopy, gravimetric analysis, contact angle and thickness measurement. Initial reaction with KOH transforms the polyimide surface to a potassium polyamate surface. The reaction of the polyamate surface with HC1 yields a polyamic acid surface. Upon curing the modified surface, the starting polyimide surface is produced. The depth of modification, which is measured by a method using an absorbance-thickness relationship established with ellipsometry and ER IR, is controlled by the KOH reaction temperature and the reaction time. Surface topography and film thickness can be maintained while a strong polyimide-polyimide adhesion is achieved. Relationship between surface structure and adhesion is discussed. 

Infrared spectroscopy experiments are performed at the University of the Saarland, Saarbriicken, using the external reflection absorption spectroscopy (ERAS) technique. Absorption peaks are attributed to molecular eigenvibrations which in some cases are localized at specific atom groups within the molecules. 

Figure 9 Optical setup for external reflection infrared measurements of Langmuir-Blodgett monolayers on liquid water surfaces. The arrow indicates the shuttling direction of the Langmuir trough in order to switch between the sample (monolayer on water) and the reference (pure water) position. (Reprinted with permission from Flach CR, Gericke A, and Mendelsohn R (1997) Quantitative determination of molecular chain tilt angles in mono-layer films at the air/water interface infrared reflection/absorption spectroscopy of behenic acid methyl ester. Journal of Physical Chemistry S 101 58-65 American Chemical Society.)...

Ever since the first reports of optical studies of electrochemical systems, efforts have been made to obtain infrared spectra of reaction intermediates and adsorbates. The earliest studies were based on total internal reflection using an n-type germanium electrode (transparent to IR radiation), and OTTLE systems using gold minigrids sandwiched between NaCl plates. These were not particularly successful, however, and it is only recently that these configurations have again been used, this time for Fourier Transform spectroscopy [29,30]. Undoubtedly the most successful technique has been potential modulated external reflectance IR spectroscopy [31]. 

Reflectance spectroscopy in the infrared and visible ultraviolet regions provides information on electronic states in the interphase. The external reflectance spectroscopy of the pure metal electrode at a variable potential (in the region of the minimal faradaic current) is also termed electroreflectance . Its importance at present is decreased by the fact that no satisfactory theory has so far been developed. The application of reflectance spectroscopy in the ultraviolet and visible regions is based on a study of the electronic spectra of adsorbed substances and oxide films on electrodes. 

The three most commonly applied external reflectance techniques can be considered in terms of the means employed to overcome the sensitivity problem. Both electrically modulated infrared spectroscopy (EMIRS) and in situ FTIR use potential modulation while polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) takes advantage of the surface selection rule to enhance surface sensitivity. 

Electrically modulated infrared spectroscopy, ( EMIRS). In all three external reflectance approaches the signal processing technique serves two purposes (a) to remove the contributions to the reflected ray that do not change, e.g. the detector response, the source emission envelope, the solvent,... 

FTIR-ERS Fourier Transform Infrared external reflection spectroscopy... 

---