First-principles study of the crystal and magnetic structures of multiferroic CuOCl.

Recently, the discovery of multiferroicity in pyrochlore-like compound CuOClhas generated significant interest, and several studies have been performed in this area. This transition metal oxychloride is unique because the divalent copper atoms create anS=1/2correlated insulator and the pyrochlore lattice tends to frustrate spins. From neutron powder diffraction measurements, an incommensurate magnetic order of the ordering vectorq=(0.827,0,0)emerges below the Néel temperature of 70 K. At this temperature or slightly above, ferroelectricity (FE) or antiferroelectricity, accompanying a lattice distortion, has been observed. Experimentally, some discrepancies remain. In this paper, we report our first-principles simulation results by evaluating the possible lattice and spin spiral states. We found that thestructure is not more stable thanFdd2(a), which is supported by our reexamination of the x-ray diffraction data. In addition, we find that after we include magnetism in the calculation, it predicts that theFdd2(a)lattice with a helical (proper screw) spin structure is energetically more stable than other spin configurations. Our results indicate charge-order-driven FE that subsequently induces magnetism.