Infrared reflection-absorption spectrum

Figure 14. Reflection-absorption infrared spectra obtained from a y-APS film deposited on an iron substrate from a 1% aqueous solution at pH 10.4 (A)—before and (B)—after exposure to X-ray irradiation and a UHV environment for 45 minutes in an XPS experiment.

This chapter has been organized by considering several aspects. An introduction concerning the relevance of the electronic properties and applications of the azamacrocycles related to surface phenomena as well as the general aspects and characteristics of the vibrational techniques, instruments and surfaces normally used in the study of the adsorbate-surface interaction. The vibrational enhanced Raman and infrared surface spectroscopies, along with the reflection-absorption infrared spectroscopy to the study of the interaction of several azamacrocycles with different metal surfaces are discussed. The analysis of the most recent publications concerning data on bands assignment, normal coordinate analysis, surface-enhanced Raman and infrared spectroscopies, reflection-absorption infrared spectra and theoretical calculations on models of the adsorbate-substrate interaction is performed. Finally, new trends about modified metal surfaces for surface-enhanced vibrational studies of new macrocycles and different molecular systems are commented. 

Reflection-absorption infrared spectra (RAIRS) are in general recorded with P-polarized light at different incident radiation angles in the range 30-80°, by using commercial variable angle accessory mounted on the IR optical bench. 

Among the vibrational modes of a molecule (or a part of it) adsorbed onto the metal surface, only those modes having transition dipole moments perpendicular to the metal surface can interact with the infrared ray polarized parallel to the plane of incidence, thereby giving rise to characteristic infrared absorption bands. The vibrational modes which have transition dipole moments parallel to the metal surface cannot be observed in the reflection-absorption infrared spectrum. These reflection-absorption phenomena are sometimes referred to as the surface selection rule. 

Whereas ATR spectroscopy is most commonly applied in obtaining infrared absorption spectra of opaque materials, reflection-absorption infrared spectroscopy (RAIRS) is usually used to obtain the absorption spectrum of a thin layer of material adsorbed on an opaque metal surface. An example would be carbon monoxide adsorbed on copper. The metal surface may be either in the form of a film or, of greaf imporfance in fhe sfudy of cafalysfs, one of fhe parficular crysfal faces of fhe mefal. 

This technique is used to study thin (down to submonolayer) films adsorbed on reflective substrates such as metals. Experimentally it involves measuring the change in the reflectance spectrum of the substrate that accompanies thin film formation. Various acronyms for the technique are used infrared reflection—absorption spectroscopy (IRRAS, IRAS) and reflection—absorption infrared spectroscopy (RAIRS). The Basics of IRRAS spectra are described in Chapter 5.2. 

Observation of absorption bands due to LO phonons in RAIR spectra of thin, silica-like films deposited onto reflecting substrates demonstrates an important difference between RAIR and transmission spectra. Berreman has shown that absorption bands related to transverse optical (TO) phonons are observed in transmission infrared spectra of thin films obtained at normal incidence [17]. However, bands related to LO phonons are observed in transmission spectra of the same films obtained at non-normal incidence and in RAIR spectra. Thus, it is possible for RAIR and transmission spectra of thin films of some materials to appear very different for reasons that are purely optical in nature. For example, when the transmission infrared spectrum of a thin, silica-like film on a KBr disc was obtained at normal incidence, bands due to TO phonons were observed near 1060,790,and450cm [18]. 

Specular reflectance infrared involves a mirrorlike reflection producing reflection measurements of a reflective material or a reflection-absorption spectrum of a film on a reflective surface. This technique is used to look at thin (from nanometers to micrometers thick) films. 

As a result, the depth of penetration, or effective pathlength, will be higher the greater X or the smaller the frequency. Therefore, an interferogram (raw infrared spectrum) is a measure of the attenuation of a trans fat test sample of the totally internally reflected infrared light. The interferogram of a reference background material (trans-free fat) is similarly measured. These are subsequently used to obtain an absorption spectrum. 

Figure 11. (a) Carbonyl absorption region of stearyl thioglycolate (b) stearyl thioglycolate on a Cu20 mirror, reflectance infrared spectrum (81° grazing angle, 4 cm-1 resolution, 2000 scans). 

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