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In general, a signal averaging of several hundred interferometric scans which takes minutes is needed to achieve a monolayer sensitivity. Even for a system highly optimized for CO studies (see for example: Leung, L. H.; Weaver, M. J. J. Phys. Chem. 1988, 92, 4019), it takes 15 s to collect a spectrum. Moreover, in in situ IR reflection spectroscopy where an external reflection mode is employed, the electrode is pushed against the IR window, forming a thin electrolyte layer of a few microns to minimize the absorption by the bulk medium. A time constant of a few tenths of a second is commonly observed for such a configuration in the absence of electroactive species due to a large iR drop along with the electrode surface, which causes a highly nonuniform current distribution particularly in the case of faradaic processes involving solution phase species. Thus, a kinetic study is severely limited.
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The sweep rate is slow enough to have the saturation coverage as early as 0.30 V in the negative sweep. If it is not saturated, the SHG signal should increase since CO adsorbs continually in this potential range
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The sweep rate is slow enough to have the saturation coverage as early as 0.30 V in the negative sweep. If it is not saturated, the SHG signal should increase since CO adsorbs continually in this potential range.
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30
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85033050136
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note
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A phase difference between the Pt background contribution and the adsorbate contribution is expected since they are complex numbers. In the case of Pt contacting an aqueous solution, the background contribution is small enough to ignore the phase difference. The error caused by the simple subtraction of this background intensity for easy mathematical treatment of the data would not be serious. However, it is not possible to obtain the background intensity in the hydrogen region. Nevertheless, the same intensity as in the DL region was assumed.
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31
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0000705807
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(a) It was also predicted theoretically that bridged CO is relatively favored in this potential region. See for example: Anderson, A. B.; Awad, M. K. J. Am. Chem. Soc. 1985, 107, 7854.
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Awad, M.K.2
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(b) Kitamura, F.; Takahashi, M.; Itoh, M. J. Phys. Chem. 1988, 92, 3320.
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(a) Bertel, E.; Memmel, N.; Rangelov, G.; Bischler, U. Chem. Phys. 1993, 177, 337.
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0037979897
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λOH or CHO are short-lived species and these species are not believed to affect the current analysis. For such findings refer to: (a) Iwasita, T.; Vielstich, W.; Santos, E. J. Electroanal. Chem. 1987, 229, 367.
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Iwasita, T.1
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Santos, E.3
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