Magnetically induced electronic ferroelectricity in half-doped manganites

Using a joint approach of density functional theory and model calculations, we demonstrate that a prototypical charge ordered half-doped manganite La1/2Ca1/2MnO3 is multiferroic. The combination of a peculiar charge-orbital ordering and a tendency to form spin dimers breaks the inversion symmetry and leads to a ferroelectric ground state with a polarization up to several μC/cm2. The presence of improper ferroelectricity does not depend on the hotly debated structural details of this material: in the Zener-polaron structure we find a similar ferroelectric response with a large polarization of purely magnetic origin.