Magnetic oxygen in transition metal oxides: A case study of Ba2CoO4

Abstract

Transition metal oxides (TMOs) exhibit exotic magnetic properties in both naturally formed and artificially structured materials, often difficult to understand in conventional wisdom. Magnetic insulator Ba2CoO4 has mystified the community, because the CoO4 tetrahedron appears to be completely isolated with the nearest Co atoms far apart (~5 Å), making it difficult to account for long-range magnetic ordering seen experimentally using only Co. By theoretically investigating magnetism and relating our findings to experimental observations in bulk Ba2CoO4, we illustrate for the first time that the magnetic moment on oxygen atoms are the origin of the unexpected long-range magnetic ordering and low magnetic dimensionality. We find that the magnetic moment is not only localized on Co atoms, as assumed in all conventional data analysis, but also distributed on its tetrahedrally-coordinated O atoms. The total magnetic moment of the CoO4 building block is 4.63μB, with the magnetic moment on Co being only 3.08μB. Therefore, the magnetic building block is CoO4, not Co. Our first principles calculations are capable of explaining the origin of the unique magnetic response, including the presence of long-range magnetic ordering with two-dimensional character and a one-dimensional magnetoelastic behavior. Having oxygen contribute to the magnetic moment may be identified as a universal property of magnetic TMOs, which would require a reconsideration of conventional models.