Self-Consistent Field Calculations of X-Ray Emission Spectra of Surface Adsorbates and Polymers

Abstract

We use modern self-consistent field methods for simulating X-ray emission spectra of surface adsorbates and polymers. Energies and intensities are computed from separately optimized wave functions with full core hole relaxation, where the surfaces and polymers are modelled by, respectively, clusters and oligomers. X-ray intensities are evaluated both from the relaxed wave functions and from ground state frozen orbitals in order to test the validity of the local selection- and the initial and final state rules, and, in the polymer case, to test band theory versus exciton theory interpretations of X-ray emission spectra. We review examples of calculations on surface adsorbates (CO/Cu(100) and C 6 H 6 /Cu(100)) and polymers (the polyene sequence).