Long Range Charge Ordering in Magnetite Below the Verwey Transition

Abstract

The crystal structure of Fe3O4 below the 122 K Verwey transition has been refined using high-resolution X-ray and neutron powder diffraction data. The refinements give direct evidence for charge ordering (CO) over four independent octahedral Fe sites, two with a charge of +2.4 and the other two of +2.6. CO schemes consistent with our model do not meet the widely-accepted Anderson condition of minimum electrostatic repulsion. Instead we propose that CO is driven primarily by a [001] electronic instability, which opens a gap at the transition through a charge density wave mechanism.