Magnetic dipolar and electric quadrupolar effects on the Mössbauer spectra of magnetite above the Verwey transition

Mössbauer spectroscopic studies (⁵⁷Fe) of powdered magnetite have been undertaken between 120 K and 880 K. Below the magnetic transition temperature (T_C=839.5 K) three six-line patterns have been fitted to our experimental spectra. The broadening of the B-pattern is explained by two magnetically non-equivalent B-site irons, suggesting broadening due to electron hopping to be negligible. In the paramagnetic state the electric quadrupole splittings of iron at A-and B-sites are found to be constant, independent of temperature, having the values zero and 0.16 mm/s, respectively. The centroid shifts, on the other hand, show above 700 K large deviations from the calculated second order Doppler shift. It is proposed that the deviations arise from a variation in band overlap. The temperature variation of the magnetic fields is found to be proportional to the sublattice magnetization. The difference in the magnetic fields at the two non-equivalent B-sites is measured to be 1.1 T at 310 K.