A relativistic self-consistent Dirac-Slater model has been used in a study of the electronic structure of 5 d-metal hexafluorides. Experimental absorption spectra have been compared with calculated energies obtained as one-electron energy differences. The calculated "crystal field" splitting between the relativistic analog of t2 g and eg levels, as well as spinorbit splitting of the t2 g level, has been found to be in good agreement with experimental data. Ionization energies which agree well with available spectra have been calculated using a transition state procedure. From a Mulliken population analysis of the molecular levels and ground state charge densities the validity of the classical crystal-field model is discussed.
ASJC Scopus subject areas
- Nuclear and High Energy Physics