The electronic structure of the vanadate and chromate ions as calculated by the MS Xα method

Abstract
Using the MSXα method, calculations of the electronic structure of the tetrahedral VO3−4 and CrO2−4 complexes have been carried out. The choice of the MSXα parameters and their influence on the results is discussed. The calculations are done in such a way so as to allow a full comparison with the corresponding results obtained by Johnson for the MnO4 complex. The calculated electronic structures of the vanadate and the chromate ions are compared with the x‐ray emission spectra and a new assignment of the spectral bands is proposed. The transition state procedure is used to calculate both ionization energies and optical transition energies. The results agree well with the observed ESCA and optical spectra, the agreement being better than that previously obtained from ab initio and semiempirical calculations.