Spin-Polarized Ground States and Ferromagnetic Order Induced by Low-Coordinated Surface Atoms and Defects in Nanoscale Magnesium Oxide

We investigate the effect of low-coordinated surface atoms on the defect-induced magnetism in MgO nanocrystallites using hybrid density functional theory calculations. It has been demonstrated that when Mg vacancies are introduced at the corners of cube-like MgO clusters, a magnetic state becomes lower in total energy than the nonmagnetic singlet state by 1-2 eV, resulting in the spin-polarized ground state. The spin density is not only located at the surrounding O atoms neighbor to the corner Mg vacancy site but is also extended to the distant (1 nm or longer) low-coordinated surface O atoms along the <110> directions. This directional spin delocalization allows a remote Mg vacancy-Mg vacancyinteraction, eventually leading to a spontaneous long-range ferromagnetic interaction.

Symmetry and Nonstoichiometry as Possible Origin of Ferromagnetism in Nanoscale oxides

We show through density functional theory calculations that extended magnetic states can inherently occur in oxides as the size of the crystals is reduced down to the nanometer scale even when they do not explicitly include intrinsic defects. This is because in nanoscale systems crystallographically perfect crystallites paradoxically result in nonstoichiometric compositions owing to the finite number of constituting atoms. In these structurally perfect but stoichiometrically imperfect nanocrystallites, the spin-triplet state is found to be more stable than the spin-singlet state, giving rise to an extended spin distribution that expands over the entire crystal. According to this picture, long-range magnetic order arises from the combined effect of crystal symmetry and nonstoichiometry that can coexist exclusively in nanoscale systems. The idea can also give reasonable explanations for the unprecedented ferromagnetic features observed commonly in nanoscale oxides, including ubiquity, anisotropy, and diluteness.