Two paramagnetic iron states at the Verwey phase transition in magnetite

At the Verwey phase transition (VPT) region a wide line of the ferromagnetic resonance (FMR) and a narrow EPR spectrum were observed. The EPR line at 125 K occurred and then disappeared below 85 K. This unexpected phenomenon is observed only if iron charge state transformation is present. Simulation of both FMR as well as EPR spectra has indicated the presence of two different iron clusters in the Fe3O4 structure. Best fit of both spectra yielded g(eff) = 2.4 and 4.1 for FMR, and g(EPR) = 2.8 and 3.4 for EPR. The presence of two-component (EPR, FMR) spectra at about T-V is due to a frustration of charge distribution in the B-sublattice as a result of the orthorhombic Pmca pseudosymmetry constraints on the atomic positions in monoclinic symmetry cell P2/c. The paramagnetic (EPR) center observed is an admixtured Fe2+ state in antiferromagnetically ordered A-sublattice ferromagnetically coupled with the B-lattice. Two paramagnetic defects observed (EPR) of localized spin states are evoked by two valency states of Fe-2.4 and Fe-2.6 below T-V. They can originate from two types of Fe4O4 cubes: "electron-rich" and" electron-poor" at a ratio 3:1 [J.P. Wright, J.P. Attfield, P.G. Radaelli, Phys. Rev. Lett. 87 (2001) 266401; Phys. Rev. B 66 (2002) 214422] or from two types of bond dimerization (H. Seo, M. Ogata, H. Fukuyama, Phys. Rev. B65 (2002) 85107). (c) 2005 Elsevier B.V. All rights reserved.