Charge-orbital ordering and Verwey transition in magnetite

Local density approximation + Hubbard U (LDA + U) band structure calculations reveal that magnetite (Fe3O4) forms an insulating charge-orbital-ordered state below the Verwey transition temperature. The calculated charge ordering is in good agreement with that inferred from recent experiments. We found an associated t(2g) orbital ordering on the octahedral Fe2+ sublattice. Such an orbital ordering results primarily from the on-site Coulomb interaction. This finding unravels such fundamental issues about the Verwey transition as the mechanism for the charge ordering and for the formation of the insulating gap, as well as the nonobedience of the Anderson's criterion for the charge ordering.     

Magnetocrystalline anisotropy of magnetite

The spin reorientation temperature T(SR) of stoichiometric Fe(3)O(4), as well as of magnetite with a small number of vacancies and magnetite containing a low concentration of Ti, Zn, Al and Ga was measured on single-crystal samples using the ac susceptibility. In the same experiment the temperature T(V) of the Verwey transition was also found. The results show that a correlation between T(SR) and T(V) exists. The electronic structure of the compounds studied was determined using the density-functional-based GGA + U method. For stoichiometric magnetite the first and second cubic anisotropy constants were calculated, while for magnetite with defects the distribution of electron density using the 'atoms in molecules' approach was determined. Based on a combination of experimental results with the electronic structure calculations an explanation of the temperature dependence of the magnetocrystalline anisotropy of magnetite is suggested.     

Verwey相变处Fe3O4的结构、磁性和电输运特性

作为典型的金属–绝缘体转变,Fe3O4的Verwey相变蕴涵的丰富物理现象与微观机制,因而受到了人们的广泛关注.在Verwey相变处,Fe3O4的晶体结构、电子结构以及磁各向异性等均发生转变,但其磁基态并未发生改变.与其他强关联体系相比,Fe3O4的Verwey相变不需要考虑磁交换耦合作用的变化,有利于揭示强关联体系中金属–绝缘体转变的物理本质.本文从晶体结构、电荷有序、电输运特性、磁性和铁电特性等方面简要地介绍了Fe3O4的Verwey相变的研究历史和现状.     

Magnetite, a model system for mixed-valence oxides, does not show charge ordering

We have investigated the charge ordering (CO) in magnetite below the Verwey transition. A new set of half-integer and mixed-integer superlattice reflections of the low-temperature phase have been studied by x-ray resonant scattering. None of these reflections show features characteristic of CO. We demonstrate the absence of CO along the c axis with the periodicity of either the cubic lattice q=(001) or the doubled cubic lattice q=(001/2). This result suggests that the Verwey transition is caused by strong electron-phonon interaction instead of an electronic ordering on the octahedral Fe atoms.     

Zener double exchange from local valence fluctuations in magnetite

Magnetite (Fe3O4) is a mixed valent system where electronic conductivity occurs on the B site (octahedral) iron sublattice of the spinel structure. Below T(V)=123 K, a metal-insulator transition occurs which is argued to arise from the charge ordering of 2+ and 3+ iron valences on the B sites (Verwey transition). Inelastic neutron scattering measurements show that optical spin waves propagating on the B site sublattice (approximately 80 meV) are shifted upwards in energy above T_{V} due to the occurrence of B-B ferromagnetic double exchange in the mixed valent phase. The double exchange interaction affects only spin waves of Delta(5) symmetry, not all modes, indicating that valence fluctuations are slow and the double exchange is constrained by short-range electron correlations above T(V).     

Verwey transition in spin polarization of field-emitted electrons from 〈1 1 0〉-oriented single crystal magnetite whisker

We measured temperature dependence of a spin polarization of field-emitted electrons from a single-crystalline magnetite (Fe₃O₄) whisker with 〈1 1 0〉 orientation. The spin polarization of emitted electrons began to increase above 130 K corresponding to the temperature of Verwey point (T_v). The increase is considered as reflection of the change of the spin state near the Fermi level due to the Verwey transition. Our experimental results support a localization of t_2g orbital electrons below the Verwey point and a model of charge ordering for magnetite.     

Direct observation of t2g orbital ordering in magnetite

Using soft-x-ray diffraction at the site-specific resonances in the Fe L2,3 edge, we find clear evidence for orbital and charge ordering in magnetite below the Verwey transition. The spectra show directly that the (001/2) diffraction peak (in cubic notation) is caused by t2g orbital ordering at octahedral Fe2+ sites and the (001) by a spatial modulation of the t2g occupation.     

Optic spin-waves in magnetite near the Verwey transition

The energies of optic spin waves at a zone centre and a (001) zone boundary have been measured in a natural crystal of magnetite at temperatures in the neighbourhood of the Verwey transition. The energies of these spin waves increased by 0.5 ± 0.4and 0.9 ± 0.5 meV respectively on cooling through the transition and therefore do not exhibit a strong change as a consequence of the ordering of the Fe²⁺ and Fe³⁺ ions at the transition.     

Macroscopic strain-coupling induced symmetry change in Fe3O4

The Verwey transition in Fe₃O₄ at 120°K is accompanied by symmetry change believed to be from cubic to orthorhombic,¹ although the exact symmetry of the low temperature magnetite as revealed by recent neutron-diffraction² and electron microscopy³ seems of a symmetry lower than the orthorhombic. In this communication, we shall only be concerned, with the aspects of possible symmetry change necessitated by degeneracy removal of the ground state wave functions, as a result of macroscopic strain coupling of the static Jahn-Teller type. No attempt will be made to include Verwey ordering, which is the object of a future paper.     

Charge-ordering signatures in the optical properties of beta-Na0.33V2O5

Temperature dependent optical spectra are reported for beta-Na0.33V2O5. The sodium ordering transition at T(Na)=240 K and, in particular, the charge ordering transition at T(MI)=136 K strongly influence the optical spectra. The metal-insulator transition at T(MI) leads to the opening of a pseudogap ( variant Planck's over 2pi omega=1700 cm(-1)) and to the appearance of a large number of optical phonons. These observations and the presence of a midinfrared band (typical for low dimensional metals) strongly suggest that the charge carriers in beta-Na0.33V2O5 are small polarons.     

Charge ordering due to magnetic symmetry breaking

It is argued that both transitions observed in 50% doped manganites, at the Néel temperature (T(N)) and the so-called charge ordering temperature (T(CO)), are magnetic. T(N) corresponds to the order-disorder transition, which takes place between ferromagnetic zigzag chains, while the coherent motion of spins within the chains is destroyed only around T(CO). The magnetic structure below T(CO) is highly anisotropic. It is dressed by the lattice distortion and leads to the huge anisotropy of the electronic structure, which explains stability of this state as well as the form of the charge-orbital pattern above T(N). The type of phase transition at T=T(N) is determined by lattice interactions.     

Mössbauer spectroscopy study of iron oxide nanoparticles obtained by spray pyrolysis

Mössbauer spectroscopy was used in this study to investigate magnetite nanoparticles, obtained by spray pyrolysis and thermal treatment under H₂ reduction atmosphere. Room temperature XRD data indicate the formation of magnetite phase and a second phase (metallic iron) which amount increases as the time of reduction under H₂ is increased. While room temperature Mössbauer data confirm the formation of the cubic phase of magnetite and the occurrence of metallic iron phase, the more complex features of 77 K-Mössbauer spectra suggest the occurrence of electronic localization favored by the different crystalline phase of magnetite at low temperatures which transition to the lower symmetry structure should occur at T ～120 K (Verwey transition).     

Origin of the Verwey transition in magnetite

Comprehensive x-ray powder diffraction studies were carried out in magnetite in the 80-150 K and 0-12 GPa ranges with a membrane-driven diamond anvil cell and helium as a pressure medium. Careful data analyses have shown that a reversible, cubic to a distorted-cubic, structural transition takes place with increasing pressure, within the (P,T) regime below the Verwey temperature TV(P). The experimental documentation that TV(P)=Tdist(P) implies that the pressure-temperature-driven metal-insulator Verwey transition is caused by a gap opening in the electronic band structure due to the crystal-structural transformation to a lower-symmetry phase. The distorted-cubic insulating phase comprises a relatively small pressure-temperature range of the stability field of the cubic metallic phase that extends to 25 GPa.     

Effect of copper doping on charge ordering in La1/3Ca2/3Mn1 ? y Cu y O3 (0 ≤ y ≤ 0.07)

The effect of copper doping on charge-orbital ordering in La_1/3Ca_2/3Mn_{1 − y} Cu _y O₃ (0 ≤ y ≤ 0.07) is studied by measuring the temperature dependences of the magnetization, the electrical resistivity, and the heat capacity in combination with an electron microscopic investigation of the structure. It is demonstrated that copper doping leads to a lowering of the charge ordering temperature T _CO and that this decrease is proportional to the decrease in the Mn³⁺ ion concentration. In the temperature range 5–300 K, the semiconducting pattern of the electrical resistivity persists for all values of 0 ≤ y ≤ 0.07. Electron microscope studies have shown that the presence of copper suppresses the formation of a regular superstructure, which is characteristic of the undoped starting compound, beginning already from low concentrations (y = 0.01). Differential scanning calorimetry revealed a substantial decrease in the transition entropy at the onset of charge ordering in copper-doped samples as compared to the starting compound. Doping with copper destroys long-range charge-orbital ordering and retains apparently only short-range order. Original Russian Text ? T.S. Orlova, J.Y. Laval, Ph. Monod, V.S. Zakhvalinskiĭ, V.M. Egorov, Yu.P. Stepanov, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 1, pp. 91–97.     

Enhanced pressure dependence of magnetic exchange in A2+[V2]O4 spinels approaching the itinerant electron limit

We report a systematic enhancement of the pressure dependence of T(N) in A(2+)[V(2)]O(4) spinels as the V-V separation approaches the critical separation for a transition to itinerant-electron behavior. An intermediate phase between localized and itinerant-electron behavior is identified in Zn[V(2)]O(4) and Mg[V(2)]O(4) exhibiting mobile holes as large polarons. Partial electronic delocalization, cooperative ordering of V-V pairs in Zn[V(2)]O(4) below T(s) approximately T(N) and dT(N)/dP<0, signals that lattice instabilities associated with the electronic crossover are a universal phenomenon.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Substrate effects on the verwey transition of thin magnetite films1

The Verwey transition in magnetite thin films has been investigated by measuring the temperature dependence of the sheet resistivity. Substrate-induced stresses raise the transition temperature above the 119.4°K reported for bulk magnetite. The ratio of the resistances of the two phases at the transition temperature is independent of the substrate and proportional to the thickness of the sample, suggesting that a 600–1200 Å surface layer remains in the high conductivity phase at all temperatures.     

Oxidized magnetosomes in magnetotactic bacteria

Single domain magnetite particles formed in chain assemblies by magnetotactic bacteria (MTB) are taken as proxy in inferring environmental and Earth's magnetism. The reliable use of magnetosomes in MTB, or their fossil remains (magnetofossils), requires that they are unaffected by oxidation. Here we present experimental data from saturation isothermal remanent magnetization (SIRM) and ferromagnetic resonance spectroscopy (FMR) between room temperature and 10 K, which were applied to detect oxidation in intact MTB. The distinction of non-oxidized from oxidized MTB-assemblies is based mainly on two different characteristic physical properties: (i) the intrinsic Verwey transition in pure magnetite, and (ii) blocking of spins of nano-sized products formed during oxidation at the surface or the interior of the magnetosomes. Suppression of the Verwey transition due to oxidation prevents the shift of the anisotropy axes, which in turn conserves the anisotropic properties at room temperature down to low temperature. The presented methodology assures a distinction between non- and oxidized magnetite assemblies, with pronounced certainty, unlike standard dc methods.     

Isotope and pressure effects on the Verwey temperature of magnetite

The isotope and pressure effects on the Verwey temperature of magnetite have been explained with the assumption that the transition is due to the condensation of an active phonon mode which is responsible for its transport properties in the high-temperature phase.     

Damping of antiferromagnetic spin waves by valence fluctuations in the double layer perovskite YBaFe2O5

Inelastic neutron scattering experiments show that spin dynamics in the charge-ordered insulating ground state of the double layer perovskite YBaFe(2)O(5) is well described in terms of e(g) superexchange interactions. Above the Verwey transition at T(V)=308 K, t(2g) double exchange-type conduction proceeds within antiferromagnetic FeO(2)-BaO-FeO(2) double layers by an electron hopping process that requires a spin flip of the five-coordinated Fe ions, costing an energy of 5S(2) approximately 0.1 eV. The hopping process disrupts near-neighbor spin correlations, leading to massive damping of zone-boundary spin waves.