Discrete Variational X α Cluster Calculations. III. Application to Transition Metal Complexes

Abstract

The discrete variational cluster calculations for perovskite type compounds KMeF 3 (Me=Cr, Mn, Fe, Co, Ni and Cu) and manganese dihalides MnX 2 (X=F, Cl and Br) have been made using the spin-polarized X α scheme. The calculated values of 10 D q and the transferred hyperfine constants are in good agreement with experiment. The d level splitting by the spin polarization is in accordance with the estimation from experimental Racah parameters. The level structure of the cluster is greatly improved by taking into account the potential from ions outside of the cluster, and shows good agreement with valence state XPS spectrum. The calculated excitation energies from ligand p to empty d and to conduction band can explain very well the u.v. spectra for MnX 2 . The halogen 3 d and 4 d are found to be important in level structures both for valence and lower excited regions of MnCl 2 and MnBr 2 .