Mössbauer characterisation of synthetic analogues of the helvite minerals Fe4M4[BeSiO4]6X2 (M = Fe, Mn, Zn; X = S, Se)

Abstract

We report on this paper on the Mössbauer characterisation of the family of synthetic helvite analogues, FeM[BeSiO]X (M = Fe, Mn, Zn; X = S, Se). The data show iron to be present as high spin Fe(II) in tetrahedral coordination. The room temperature Mössbauer spectra are composed either by singlets or doublets with small quadrupole splitting values suggesting a small valence contribution at that temperature. From the dependence of the quadrupole splitting with temperature the separation Δ between the two e orbitals has been estimated. The values of Δ range from 46.3 cm for the material Fe[BeSiO]S to 58.2 cm for the material FeZn[BeSiO]S. The lack of long-range magnetic order observed in the Mössbauer spectra was confirmed by neutron diffraction data which suggests that the MX units are largely magnetically isolated within their cages leading to a frustrated magnet with no long range interaction for the sulfide species.