SELF-CONSISTENT-FIELD CALCULATIONS OF X-RAY-EMISSION SPECTRA OF SURFACE ADSORBATES AND POLYMERS

We use modern self-consistent field methods for simulating X-ray emiss ion spectra of surface adsorbates and polymers. Energies and intensiti es are computed from separately optimized wave functions with full cor e hole relaxation, where the surfaces and polymers are modelled by, re spectively, clusters and oligomers. X-ray intensities are evaluated bo th from the relaxed wave functions and from ground state frozen orbita ls in order to test the validity of the local selection-and the initia l and final state rules, and, in the polymer case, to test band theory versus exciton theory interpretations of X-ray emission spectra. We r eview examples of calculations on surface adsorbates (CO/Cu(100) and C 6H6/Cu(100)) and polymers (the polyene sequence).