SF6 - LARGE-SCALE AB-INITIO CALCULATIONS AND THE ASSIGNMENT OF THE PHOTOELECTRON-SPECTRUM

Calculations with a large basis set including many polarization functions are reported for SF6. The feasibility of such calculations is discussed. By adding Koopman's corrections as calculated previously to be more accurate values of the orbital energies obtained here the assignment problem of the valence photoelectron spectrum is reconsidered. The values of the ionization potentials are improved compared to the previous work but no change of ordering occurs. The disagreement in the assignment with the recent work of Gustafsson who measured partial photoionization cross sections of SF6 thus remains and remains unexplained. © 1979.