Electric field properties at cationic sites in normal, incommensurate and commensurate K2ZnCl4 crystals

The local electric properties at K and Zn sites in the normal, incommensurate and commensurate phases of K₂ZnCl₄, as derived from a numerical computation of the lattice contributions to the electric potential V(r), electric field intensityE(r) and electric field gradient tensorV _αβ(r) are reported. The numerical data obtained at each cationic position were correlated with the experimental³⁹K NMR, Cu²⁺ and Mn²⁺ EPR and⁵⁷Fe Mössbauer results in pure and doped K₂ZnCl₄. A proportionality between crystal field and zero-field splitting was taken into account for Mn²⁺, whereas for K⁺, Cu²⁺ and Fe³⁺ ions the electric field gradient is directly related to the crystal field parameter. By this comparison, on computations done in the ionic fractional charge and relaxed lattice approximations, the insertion of probe-species of iron, copper and manganese ions on off-center Zn sites is proposed. The³⁹K electric field gradient tensor calculations in the incommensurate phase fit well with the NMR data reported recently.