RAIRS vibrational losses

The success of the isotope dilution experiment for CO on Pt(lll) was accompanied by a serious difficulty in reconciling the magnitude of the shift, which determines Oy/3Q), with the intensity of the band, which also determines Oy/3Q). When due allowance is made for the resultant surface field and geometric factors (36) in RAIR spectroscopy the intensity is almost consistent with the vibrational polarizability av = 0.057 X3 (39), corresponding to the gas phase intensity, as has been concluded for CO adsorbed on copper films (40) from infrared studies and for CO on Pt(lll) (41) and Cu(100) (42) from high resolution electron energy loss spectroscopy. This value of av is an order of magnitude smaller than that deduced from the frequency shift. 

There is a number of vibrational spectroscopic techniques not directly applicable to the study of real catalysts but which are used with model surfaces, such as single crystals. These include reflection-absorption infrared spectroscopy (RAIRS or IRAS) high-resolution electron energy loss spectroscopy (HREELS, EELS) infrared ellipsometric spectroscopy. 

Since both HREELS and RAIRS are vibrational spectroscopies, and the same selection rules apply, their information contents must overlap. This is demonstrated in Fig. 8 [2], in which the HREELS and RAIRS spectra from a Cu(l 11) surface covered with about 10 molecular layers of cyclohexane at low temperature are shown. The vibrational spectra appear at the same energetic positions in both techniques, but it should be noted that whereas RAIRS has the advantage of better energy resolution HREELS is able to record spectra down to losses close to 0 cm. For reasons of IR transmission of window materials, the cutoff in RAIRS is in the region 400-800 cm". ... 

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