Identification of defect sites on MgO(100) thin films by decoration with Pd atoms and studying CO adsorption properties

CO adsorption on Pd atoms deposited on MgO(100) thin films has been studied by means of thermal desorption (TDS) and Fourier transform infrared (FTIR) spectroscopies. CO desorbs from the adsorbed Pd atoms at a temperature of about 250 K, which corresponds to a binding energy, E-b, of about 0.7 +/- 0 .1 eV. FTIR spectra suggest that at saturation two different sites for CO a dsorption exist on a single Pd atom. The vibrational frequency of the most stable, singly adsorbed CO molecule is 2055 cm(-1). Density functional clus ter model calculations have been used to model possible defect sites at the MgO surface where the Pd atoms are likely to be adsorbed. CO/Pd complexes located at regular or low-coordinated O anions of the surface exhibit consi derably stronger binding energies, E-b = 2-2.5 eV, and larger vibrational s hifts than were observed in the experiment. CO/Pd complexes located at oxyg en vacancies (F or F+ centers) are characterized by much smaller binding en ergies, E-b = 0.5 +/- 0.2 or 0.7 +/- 0.2 eV, which are in agreement with th e experimental value. CO/Pd complexes located at the paramagnetic F+ center s show vibrational frequencies in closest agreement with the experimental d ata. These comparisons therefore suggest that the Pd atoms are mainly adsor bed at oxygen vacancies.