Infrared reflectance-absorption

Szanyi J, Kuhn W K and Goodman D W 1994 CO oxidation on palladium 2. A combined kinetic-infrared reflection absorption spectroscopic study of Pd(IOO) J. Phys. Chem. 98 2978... 

KJ. Uram, L. Ng, and J.R.Yates Jr., Electrostatic effects between adsorbed species-The K-CO interaction on Ni(lll) as studied by infrared reflection - absorption spectroscopy, Surf. Sci. 177, 253-277 (1986). 

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. 

Westermark, G. and Persson, 1. (1998) Chemisorption of tertiary phosphines on coinage and platinum group metal powders. An infrared reflectance absorption spectroscopic, enhanced Raman spectroscopic and surface coverage study. Colloids and Surfaces A -Physicochemical and Engineering Aspects, 144, 149-166. 

K. and Enyo, M. (1989) Surface species produced on Pt electrodes during HCHO oxidation in sulfuric add solution as studied by infrared reflection-absorption spectroscopy (IRRAS) and differential electrochemical mass spectroscopy (OEMS)./. Electroanal. Chem., 258, 219-225. 

Watanabe, S., Inukai, J. and Ito, M. (1993) Coverage and potential dependent CO adsorption on Pt(llll), (711) and (100) electrode surfaces studied by infrared reflection absorption spectroscopy. Surf. Sci., 293, 1-9. 

Figure 6.16 Attenuated total reflection surface enhanced infrared reflection absorption spectroscopy (ATR-SEIRAS) spectra for the oxidation of 0.1 M HCOOH in 0.5 M H2SO4 on a polycrystaUine electrode. The bands at 2055 -2075 and 1800-1850 cm are assigned to linear- and bridge-bonded CO, whereas the band at 1323 cm corresponds to adsorbed formate. (Reproduced from Samjeske et al. [2006].)...

Bhzanac BB, Arenz M, Ross PN, Markovic NM. 2004b. Surface electrochemistry of CO on reconstructed gold single crystal surfaces studied by infrared reflection absorption spectroscopy and rotating disk electrode. J Am Chem Soc 126 10130-10141. 

Hoshi N, Bae IT, Scherson DA. 2000. In situ infrared reflection absorption spectroscopic studies of coadsorption of CO with underpotential-deposited lead on Pt(lll) in an aqueous acidic solution. J Phys Chem B 104 6049-6052. 

Watanabe M, Zhu Y, Uchida H. 2000. Oxidation of CO on a Pt-Fe alloy electrode studied by surface enhanced infrared reflection-absorption spectroscopy. J Phys Chem B 104 1762-1768. 

KitamuraF, Takahashi M, Ito M. 1989. Carbon monoxide adsorption on platinum (111) singlecrystal electrode surface studied by infrared reflection - absorption spectroscoy. Surf Sci 223 493-508. 

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... 

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. 

A great deal of success was attendant on the early application of PM-IRRAS to the gas/solid interface. Golden et ai (1981) reported the development of instrumentation, using conventional dispersive optics, able to record detailed infrared reflection-absorption spectra from molecules adsorbed on single-crystal Pt without any interference from the gas-phase species. 

In order to evaluate quantitatively the molecular orientation in thin LB films, several attempts have been made by using infrared reflection-absorption (RA) technique [1,2]. Recently, we have proposed a useful and convenient method combining infrared... 

---