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Title Charge, orbital and magnetic ordering in transition metal oxides
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Degree PhD
Degree Level doctoral
University/Publisher University of Edinburgh
Abstract Neutron and x-ray diffraction has been used to study charge, orbital and magnetic ordering in some transition metal oxides. The long standing controversy regarding the nature of the ground state (Verwey structure) of the canonical charge ordered material magnetite (Fe3O4) has been resolved by x-ray single crystal diffraction studies on an almost single domain sample at 90 K. The Verwey structure is confirmed to have Cc symmetry with 56 unique sites in the asymmetric unit. Charge ordering is shown to be a useful first approximation to describe the nature of the ground state, and the conjecture that Verwey made in 1939 has finally been confirmed. However, three-site distortions which couple to the orbital ordering of the Fe2+ ordered states (trimerons) are shown to provide a more complete description of the low temperature structure. Trimerons explain the rather continuous distribution of the valence states observed in magnetite below Tv, anomalous shortening of Fe-Fe distances and the off-centre distortions resulting in ferroelectricity. DFT+U electronic structure calculations on the experimental coordinates support the conclusion of this crystallographic study, with the highest electron densities calculated for those Fe-Fe distances predicated to participate in the trimeron bonds. The 6H-perovskites of the type Ba3ARu2O9 have been reinvestigated by high resolution neutron and x-ray power diffraction. The charge ordered state of Ba3NaRu2O9 has been characterised at 110 K (P2/c, a =5.84001(2) Å, b = 10.22197(4) Å, c = 14.48497(6) Å, β = 90.2627(3) °) and shown to consist of a structure with near integer charge ordering of Ru5+ 2O9 / Ru6+ 2O9 dimers. The ground state has been shown to be very sensitive to external perturbations, with a novel melting of charge ordering observed under x-ray irradiation below 40 K (C2/c, a =5.84470(2) Å, b = 10.17706(3) Å, c = 14.45866(5) Å, β = 90.2151(3)-° at 10 K). High pressure studies reveal that the Ru-Ru intra-dimer distance may dictate the response of the system to pressure. Empirical trends in the Ba3ARu2O9 series of compounds have shown that change in ‘chemical pressure’ in these systems may be rationalised in terms of Coulomb’s law. In A = La and Y the magnetic ordering is shown to be FM within the Ru2O9 dimers (1.4(2) μB and 0.5(1) μB, respectively per Ru), representing the first case of intra dimer FM coupling reported in a system containing face-sharing RuO6 octahedra . The overall AFM coupling of the dimers implies an as yet unobserved breaking of the parent symmetry. In A = Nd, a complex competition between the crystal field effect of Nd3+ and the magnetic ordering of the Ru2O9 FM moments has been observed, leading first vi to FM order of Nd at 25 K (1.56(7) μB) followed by ordering of Ru moments (0.5(1) μB) and a spin reorientation transition of Nd moments at 18 K. In A = Ca, the formation of a singlet ground state is observed in Ru2O9 rather than the expected AFM coupling and below 100 K Ba3CaRu2O9 is diamagnetic. All five systems indicate that the Ru2O9 dimer is the…
Subjects/Keywords 661; transition metal oxides ; Charge ordering ; Verwey structure ; orbital ordering ; trimerons
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Country of Publication uk
Record ID handle:1842/7828
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Date Indexed 2020-06-17

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…27 1.4.4. Basis function .......................................................................................... 28 Section B: The Verwey structure of Magnetite ..................................................................... 30 2…

…Introduction to spinels and the Verwey transition .................................................... 30 2.1. Spinels and magnetite ...................................................................................... 30 2.2. Magnetite and the Verwey

…41 Solution of the Verwey structure of magnetite by single crystal x-ray diffraction... 45 3.1. Experimental design and crystallographic considerations ............................... 45 3.1.1. Extinction, multiple scattering and saturation…

…crystal and data quality ..................................................... 59 3.3.3. Validation of the final model of the Verwey structure ............................ 66 3.4. Discussion: Rationalisation of structural distortions…

…91 Electronic structure calculations on the Verwey ground state .................................. 93 4.1. Calculation details and convergence test ......................................................... 93 4.2. Interpretation of calculated…

…177 Appendix A : Full details of structural refinement models for Fe3O4 ....................... 177 Appendix B : Details of the distortion mode analysis for the Verwey structure ...... 202 Appendix C : Details of single crystal and powder…

…QTot - Total integrated charge rA – Ionic radii of ion A RE – Rare earth RMT – Muffin tin sphere radius SCF – Self-consistent field SOP – Secondary order parameters t – Goldschmidt tolerance factor Tv – Verwey transition temperature Tc – Phase…

…illustrated with relevant examples. 1.1.1. Charge Ordering The notion of charge ordering was first postulated by Winger in 1938.1 Independently, charge ordering (CO) was proposed by Verwey in 1939 on observation of a semiconductor 1 Chapter 1…

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