On the adsorption sites for CO on the Rh(111) single crystal surface

High resolution photoemission applied to the C 1s and Rh 3d core levels has been used to investigate the adsorption sites at low temperature of CO on the Rh(111) single crystal surface as a function of CO coverage. Two different sites are found to be occupied by the CO molecules. At coverages up to 0.5 monolayers the majority of the molecules are found to adsorb in on-top sites whereas at higher coverages three-fold hollow sites become increasingly populated. The different C 1s binding energy of the CO molecules in these two sites makes it possible to measure diffraction induced intensity variations versus photon energy in a site specific manner. The saturation (2 x 2)-3CO structure formed at a coverage of 0.75 monolayers is argued to contain one on-top and two three-fold hollow molecules per unit cell.