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
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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 physically
significant unit in these systems when considering structural trends and the ordering of
charge, spin and orbital degrees of freedom
