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Core binding energies of selected atoms, ions, and molecules

Thesis/Dissertation ·
OSTI ID:5795658

The following topics are addressed: (1) improved theoretical calculations of core level binding energies in atoms and ions using the ..delta..SCF method; and (2) several experimental studies of the core level photoelectron spectra acquired from selected free molecular species produced at elevated temperatures. The study of free atoms by means of photoelectron spectroscopy was limited due to the experimental difficulties involved in the production of atoms in the context of an electron spectroscopy experiment. State-of-the-art Hartree-Fock ..delta..SCF calculations were used extensively in calculating core level binding energies of free atoms. Calculations based on the Dirac-Fock ..delta..SCF method, which includes the effects of relativity were found to yield core level binding energies that are more accurate compared with the experimental values available. Calculations were also performed on selected ions. The remaining discrepancy following a Dirac-Fock calculation is due to electron correlation; this was calculated semiempirically for ions isoelectronic with the rare gases. Another method of including correlation is discussed and employed in the calculation of core level binding energies for the Group VA atoms phosphorus and arsenic and also for the Group VIA atom selenium.

Research Organization:
Vanderbilt Univ., Nashville, TN (USA)
OSTI ID:
5795658
Country of Publication:
United States
Language:
English