The kinetics of the adsorption system CO/Pt(111) has been studied by time-resolved high-resolution x-ray photoelectron spectroscopy using third generation synchrotron radiation at BESSY II. CO is dosed by a supersonic molecular beam device which allows for a high sample pressure (here up to 10−6 mbar) and a fast switching of the pressure. The site-specific occupation of CO adsorbed on on-top and bridge sites is determined quantitatively from C 1s spectra, which can be taken with a minimum collection time of 1.5 s per spectrum. Based on the observation of thermal equilibrium between the two sites, we perform a phenomenological analysis of the data, assuming a constant binding energy difference ΔE. From the on-top/bridge occupation ratio as a function of coverage obtained by uptake measurements we extract a value of ΔE=41 meV. With the same ansatz, ΔE is calculated from temperature-dependent measurements at a constant coverage. Finally, determination of the coverage during isothermal desorption is used to obtain the total binding energy of CO on Pt(111). Differences between our evaluation methods and literature reports are discussed.

In an effort to extend the pressure range for electron-based spectroscopies from ultrahigh vacuum into the so-called pressure gap region, we have built a new apparatus for in situ x-ray photoelectron spectroscopy up to 1mbar. The principle of the experimental setup is based on a modified hemispherical electron energy analyzer, a modified twin anode x-ray source, and several differential-pumping stages between sample region and electron detection. The reaction gas is provided in situ either by background dosing or, as a new feature, by beam dosing, using a directed gas beam from a small tube. The latter allows for higher local pressures. The performance of the new setup is discussed, deriving normalization procedures from the analysis of the attenuation of the substrate photoemission intensity by the increasing gas phase pressure. In addition, the change of the work function due to changes in surface composition can be evaluated in situ by analyzing the binding energy shift of the gas phase core-level peaks. As a first study, measurements for the pressure dependence of CO adsorption on Pd(111) between 5×10−8 and 1mbar are presented.

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