Second-sphere cations effect on spectroscopic parameters of tetrahedral and octahedral complexes in the frame work of the theory of LCAO and electronic groups

Changes in spectroscopic parameters of splitting of complex ions of transition metals under the effect of second sphere cations of alkali- and alkaline-earth metals have been investigated within the framework of the theory of LKMO and electron groups as applied to the condensed state of substances, such as melts and crystals. It has been established that if the field of the second-sphere cations is equivalent to that of the inner coordination sphere, the value of the splitting parameter of the complex ion reduces. Besides, the nature of the effect of the tetrahedral field of the second-sphere cations on the octahedral ion is established. It is shown that the effect on the splitting of complex ions reduces in the series of Li+, Na+, K+, Kb+, Cs+ with diminishing ionization potentials of the atoms