Chapter 19 - Extension of the crystal field potential beyond the one-electron model

Abstract

Within the one-electron model extended by every possible interconfiguration interactions, the entire crystal field (CF) effect can be reconstructed. However, one ought to employ the electron configurations of the whole ionic complex and consider among the excited configurations those of charge-transfer type and those referring to the ligands themselves. The initial one-configurational model corresponding to absolutely fixed configurations leads to the crystal field effect representation. All the remaining contributions are expressible by means of appropriate interconfigurational interactions. In practice, the calculations are carried out under some simplifying assumptions. From these calculations, the spectrum of energy levels in the crystal field is available. This result can be compared with the experimental data to verify adequacy of the method, but the spectrum can be put to test the effective parameterization within the one-electron model.