The effects of cationic substitutions at different concentrations within the lattice Znx Cd1-xCr2Se4 (0.35≤x≤0.58) on the electronic transfer in chromium ions are investigated. For this propose, after taking into account the exchange integrals, we use the Anderson’s-Kanamori theory of superexchange to determine the transfer integrals bσσ and bπσ . With the use of the conventional molecular orbital model the covalency-mixing parameters, λσ and λπ, the electron spin transfer coefficients, ƒ i (i=σ, π, s ), and the total charge, C, transferred from ligand to the chromium ions, are evaluated. The variation of bσσ and bσπ with x agree with the passage of the system from ferromagnetic to antiferromagnetic order. For the compound presenting re-entrant behaviour (0.45≤x≤0.58), f s exhibits anomalous. The increasing in C with x is consistent with the expected decrease in covalency of the non magnetic cation in tetrahedral site.The effects of cationic substitutions at different concentrations within the lattice Znx Cd1-xCr2Se4 (0.35≤x≤0.58) on the electronic transfer in chromium ions are investigated. For this propose, after taking into account the exchange integrals, we use the Anderson’s-Kanamori theory of superexchange to determine the transfer integrals bσσ and bπσ . With the use of the conventional molecular orbital model the covalency-mixing parameters, λσ and λπ, the electron spin transfer coefficients, ƒ i (i=σ, π, s ), and the total charge, C, transferred from ligand to the chromium ions, are evaluated. The variation of bσσ and bσπ with x agree with the passage of the system from ferromagnetic to antiferromagnetic order. For the compound presenting re-entrant behaviour (0.45≤x≤0.58), f s exhibits anomalous. The increasing in C with x is consistent with the expected decrease in covalency of the non magnetic cation in tetrahedral site
