Magnetic behaviour of synthetic Co2SiO4

Synthetic Co2SiO4 crystallizes in the olivine structure (space group ) with two crystallographically non‐equivalent Co positions and shows antiferromagnetic ordering below 50 K. We have investigated the temperature variation of the Co2SiO4 magnetic structure by means of non‐polarized and polarized neutron diffraction for single crystals. Measurements with non‐polarized neutrons were made at 2.5 K (below TN), whereas polarized neutron diffraction experiments were carried out at 70 and 150 K (above TN) in an external magnetic field of 7 T parallel to the b axis. Additional accurate non‐polarized powder diffraction studies were performed in a broad temperature range from 5 to 500 K with small temperature increments. Detailed symmetry analysis of the Co2SiO4 magnetic structure shows that it corresponds to the magnetic (Shubnikov) group Pnma, which allows the antiferromagnetic configuration (Gx, Cy, Az) for the 4a site with inversion symmetry (Co1 position) and (0,Cy,0) for the 4c site with mirror symmetry m (Co2 position). The temperature dependence of the Co1 and Co2 magnetic moments obtained from neutron diffraction experiments was fitted in a modified molecular‐field model. The polarized neutron study of the magnetization induced by an applied field shows a non‐negligible amount of magnetic moment on the oxygen positions, indicating a delocalization of the magnetic moment from Co towards neighbouring O owing to superexchange coupling. The relative strength of the exchange interactions is discussed based on the non‐polarized and polarized neutron data.