The photoelectron and optical spectra of TiCl4 and VCl4 are investigated within the framework of the Hartree‐Fock‐Slater model. The sensitivity of these spectra to choice of atomic configuration (in a non‐self‐consistent model) and exchange scaling parameter α is explored, making use of a discrete variational method previously reported. It is shown that values of α can be found to match both ionization potentials and optical transitions fairly well in the simplified one electron model based on superimposed atomic charge densities. Results of self‐consistent field models are presented, and the relationship to more rigorous theories is discussed.

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