In the chemisorption system CO/Ni(100), a comparison between available high resolution core level photoelectron spectra and spectra calculated by the INDO/CI method done for different nickel cluster sizes. A reassignment of some of the satellites is made. It is found that the asymmetry and the broadening of the main line mainly depends on substrate-substrate excitations, predominantly from the d-band to the s-band within the nickelsubstrate.
The satellite structure of the Cls and Ols photoelectron spectra of chromium hexacarbonyl Cr(CO)(6) has been calculated by the INDO/CI method and compared with available high resolution core level photoelectron spectra. A reassignment of some of the lines is made. It is found that the satellite structure in both cases is dominated by excitations from metal-ligand bonding to metal-ligand antibonding Me(3d)-pi* orbitals, and that these shake-up excitations involve a significant charge transfer to the core ionized ligand from the rest of the molecule.
Experimental high-resolution core photoelectron C1s and O1s shake-up spectra of molybdenum hexacarbonyl, Mo(CO)(6), are reported and compared with results of semiempirical INDO/CI calculations. Several hitherto unobserved peaks are identified and assigned. It is found that an intra- and inter-group classification can be used to describe the transitions. The transitions of lowest energy have Mo-CO inter-group character. Dynamical effects on the line widths of the experimental shake-up peaks are discussed. A discussion of the relevance of experimental results obtained for the Mo(CO)(6)e for CO adsorption on metal surfaces is presented.
INDO/CI calculations were used to analyze the C1s and O1s shake-up spectra of nickel tetracarbonyl, Ni(CO)4. The satellite structure in both cases is dominated by excitations from metal–ligand bonding (2Πb) to metal–ligand antibonding (2Πa) orbitals and by excitations within the core-ionized CO molecule, ΠCO—Π*CO.
A new parameterization for copper at the INDO/CI level is presented. Results for excitation energies, ionization potentials, and electron detachment energies are presented for selected copper clusters with up to ten atoms. The parameterization gives improved results for calculations of spectroscopic properties for systems with significant copper-copper interactions, such as clusters and model surfaces. Results for the Ols shakeup of CO attached to Cu(100) model surfaces for the new parameters are compared with experiments and with results obtained using the standard parameters.