A THEORETICAL-STUDY OF X-RAY PHOTOELECTRON-SPECTRA OF MODEL MOLECULES FOR POLYMETHYLMETHACRYLATE

We explore the usefulness of the delta self-consistent-field (DELTA-SCF) approximation in connection with high-resolution x-ray photoelectron spectra for component and structural analysis of organic compounds. Results for core electron binding energy shifts for model molecules of the polymethylmethacrylate polymer are presented. A previously devised method for proper self-consistent-field solutions for core hole states in molecules is evaluated. The results indicate that chemical shifts can be obtained within a few tenths of an eV. A discussion is presented on the inherent errors in the DELTA-SCF approximation, the proper corrections for zero-point vibrational energies, and the role of relaxation of core orbitals.