Type II multiferroic order in two-dimensional transition metal halides from first principles spin-spiral calculations

Abstract

Abstract We present a computational search for spin spiral ground states in two-dimensional transition metal halides that are experimentally known as van der Waals bonded bulk materials. Such spin spirals break the rotational symmetry of the lattice and lead to polar ground states where the axis of polarization is strongly coupled to the magnetic order (type II multiferroics). We apply the generalized Bloch theorem in conjunction with non-collinear density functional theory calculations to find the spiralling vector that minimizes the energy and then include spin–orbit coupling to calculate the preferred orientation of the spin plane with respect to the spiral vector. We find a wide variety of magnetic orders ranging from ferromagnetic, stripy anti-ferromagnetic, 120∘ non-collinear structures and incommensurate spin spirals. The latter two introduce polar axes and are found in the majority of materials considered here. The spontaneous polarization is calculated for the incommensurate spin spirals by performing full supercell relaxation including spinorbit coupling and the induced polarization is shown to be strongly dependent on the orientation of the spiral planes. We also test the effect of Hubbard corrections on the results and find that for most materials LDA + U results agree qualitatively with LDA. An exception is the Mn halides, which are found to exhibit incommensurate spin spiral ground states if Hubbard corrections are included whereas bare LDA yields a 120∘ non-collinear ground state.