CO/Rh(111): Vibrational frequency shifts and lateral interactions in adsorbate layers

High resolution electron energy loss spectroscopy (HREELS), low-energy electron diffraction (LEED), and thermal desorption spectroscopy (TDS) were used to study lateral interactions in the adsorbate layer of the CO/Rh(111) system. The vibrational spectra show that CO adsorbs exclusively on top at low coverage. At about half a monolayer a second adsorption site, the threefold hollow site, becomes occupied as well. A steady shift to higher frequencies of the internal C-O vibrations is observed over the whole coverage range. The frequency of the metal CO (M-CO) vibration in the on-top mode hardly shifts at low coverage. However, upon the emergence of the second adsorption site the M-CO vibrations experience a shift to lower frequencies. The population of the second site is also accompanied by the development of a low temperature shoulder in the TD spectra, indicating an increasingly repulsive interaction in the adsorbed CO layer. Vibrational spectra of isotopic mixtures of (CO)-C-12 and (CO)-C-13 were used to assess the origin of the observed frequency shifts. They confirm that frequency shifts of the C-O stretching vibration at total CO coverage of 0.33 ML in the (root 3x root3)R30 degrees structure arise purely from dipole-dipole coupling. Dilution of an isotopic species effectively suppresses frequency shifts arising from dipole-dipole coupling. Therefore, experiments with a small amount of (CO)-C-13 as a tracer to monitor the frequency shifts in the (CO)-C-12 adlayer were carried out over the entire coverage range of (CO)-C-12. The results demonstrate that dipole-dipole coupling causes the frequency shifts at low coverage (