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By Gould R.F. (ed.)

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6667 A n 100 200 vc 300 400 500 600 KINETIC ENERGY (eV1 Fig. 37. Auger spectra of adsorhed thiophenol and related compounds at Pt(ll1). (a) Clean Pt(l11); (h) 2,5-dihydroxy-4-methylhenzylmercaptan (DMBM); (c) Thiophenol (TP); (d) Pentafluorothiophenol (PFTP). 7 mM; incident beam IOOnA, 2000eV a t normal incidence. Reprinted from ref. 81. tion). The results in Fig. 36(a) are quantitatively consistent with those obtained with thin-layer electrodes (entirely in solution). Since LEED, Auger, and EELS were employed to examine the surface layer during the hour in UHV, there was evidently no appreciable beam damage to the layer.

28)], above, is representative of the behavior of a special group of adsorbates for which a reversibly electroactive adsorbed pendant is observed [57]. /////////// T///,////// The electroactivity of the adsorbed states of this group of compounds is evidently associated with the presence on the adsorbed layer of a pendant functionality which is electroactive in the unadsorbed molecule and is attached to the surface in such a way that the pendant is virtually unperturbed structurally or electronically by the surface.

In contrast, a molecule such as hydroquinone which is electroactive prior to adsorption but is strongly perturbed by adsorption (that is, by direct covalent attachment to the Pt surface) is not reversibly electroactive in the adsorbed state (Fig. 26). Accordingly, adsorbed DMBM is reversibly electroactive under almost all conditions, while adsorbed HQ is not reversibly electroactive under any conditions thus far studied. In between these two extremes is THBP, which is reversibly electroactive in one of its adsorbed states but not in the other two.

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