Calculation of Some Electronic Energy Levels of Sulfur Hexafluoride

Abstract

An attempt has been made to calculate the coefficients in LCAO molecular orbital functions of SF₆, and ionization and excitation energies of this molecule, using a self‐consistent field method. The lowest ionization potential computed is 20.1 ev. Excitation energies to some forbidden and allowed levels are obtained, but are too large to be considered trustworthy. The present treatment was restricted in detail to twelve electrons, six from the sp³d² valence configuration of sulfur, and six 2pσ of fluorine. The other electrons were treated in smoothed‐out core potentials of the sulfur and fluorine atoms. It is believed that unexpectedly large errors may have been introduced by the neglect of detailed interactions of these electrons, and that the molecular orbitals in which they might be put are of importance. The present calculation is purely theoretical and only the empirical value of the S–F bond distance has been used. All necessary integrals have been evaluated, most of them for the first time, and are collected in tables.