Temperature dependence of the 57Fe Mössbauer parameters in riebeckite

Abstract

Mossbauer spectra for two riebeckite minerals were collected at temperatures in the range 4.2 to 500 K. The magnetic-ordering temperatures were found to be 33±1 and 31±1 K respectively. Fitting the paramagnetic spectra with a discrete number of doublets (three or four) did not lead to consistent results. Instead, a superposition of an Fe3+ (M2) doublet and one distributed ferrous component was found to produce adequate fits with reasonable parameter values. For both samples, a minor fraction of ferrous ions was observed to be present at the M4 sites and for one of the samples at the M2 sites as well. The temperature variations of the center shifts were well reproduced using the Debye model of the lattice vibrational spectrum to evaluate the second-order Doppler shift. The characteristic Mossbauer temperatures were calculated to be in the range 340–390 K for Fe2+, and 520 K for Fe3+. The temperature dependences of the various ferrous quadrupole splittings could not be explained in terms of the point-charge model and assuming a temperature-independent energy-level scheme for the 5D term. It is suggested that a gradual change with temperature of the orbital-level splittings takes place. All calculations yielded a positive sign for the principal component of the electric field gradient (EFG). The spectrum recorded at 4.2 K for one of the riebeckites was fitted with a superposition of an Fe3+ and a Fe2+ hyperfine-field distribution, the latter one primarily characterizing the Fe2+ (M1) cations. The following relevant hyperfine data were calculated: Hhf=161 kOe, ΔEQ=3.11 mm/s, and Vzz<0, all referring to the maximum-propability values. For the second riebeckite at 4.2 K, an additional distributed ferrous component could independently be resolved. The two maximum-probability hyperfine fields were found to be 189 and 98 kOe and the corresponding ΔEQ values 3.10 and 2.67 mm/s. Both components exhibit a negative Vzz. The subspectra were attributed to M1 and M3 sites respectively. The Fe3+ hyperfine fields are 548+-2 kOe for both riebeckites. The different values found for the Fe3+ quadrupole shift 2ɛQ for the two samples is explained by a different angle between the hyperfine field and the EFG's principal axis. The magnetic spectra recorded at 15 K and higher, could not be reproduced adequately with reasonable parameter values.