Correlation of Zero Field Splittings and Site Distortions V. Mn²⁺ in Cs₂Zn₃S₄

Abstract

In platelets of Cs 2 Zn 3 S 4 with about 4% of the Zn substituted by Mn two nonequivalent centers of isolated Mn 2+ were observed in addition to a broad EPR signal near g = 2 which is assigned to clusters of interconnected MnS 4 units. The fine structure and hyperfine structure parameters for the single-ion centers (all in units of 1CT 4 cm -1 ) are: for centers I and II, resp. Center II arises from Zn sites of C 2 site symmetry while for center I assignment to either one of two sites with D 2 site symmetry is possible. The larger hyperfine splitting constants as well as the superposition analysis favor the larger sites which are not occupied by Zn, but are partly occupied in the analogous Mn (and Co) compounds. Superposition analysis yields the same value of + 0.12 ± 0.02 cm"' for the intrinsic zero field splitting parameter b 2 of the bridging MnS 4 units in both sites. g : is significantly higher than the free ion value indicating a higher degree of covalency than in Cds and CdGa 2 S 4 .