Thermodynamic stability and atomic and electronic structure of reduced Fe3 O4 (111) single-crystal surfaces

Magnetite (111) single-crystal surfaces prepared in situ under different reducing conditions and—as a result—with varying stoichiometries have been studied by scanning tunneling microscopy, low-energy electron diffraction, and x-ray photoemission spectroscopy. The coexistence of several surface structures has been detected, indicating only small differences in their relative stabilities. In particular, an unusual previously unreported superstructure has been found for a strongly reduced surface. Its microscopic origin is discussed against the background of recent results from scanning tunneling microscopy of the oxidized magnetite (111) surface and from ab initio thermodynamics. Partly at variance with and partly complementary to these results, we regard as driving force elastic strain due to the lateral mismatch between Fe3O4 substrate and Fe1-xO-like overlayer.