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Although discussions of structural phase transitions in prototypical ferroelectric systems with the perovskite structure, such as BaTiO_{3} and PbTiO_{3}, started almost seventy years ago, an atomic-level description of the polar characteristics as a function of temperature, pressure, and composition remains topical. Here we provide a novel quantitative description of the temperature-driven local structural correlations in PbTiO_{3} via the development of characteristic relative cationic shifts. The results give new insights into the phase transition beyond those reliant on the long-range order. The ferroelectric-to-paraelectric transition of PbTiO_{3} is realized by the extent of a stochastic polarization instability driven by a progressive misalignment instead of a complete disappearance of the local dipoles, which further suggests that such polarization instability is chemically induced at the morphotropic phase boundary of PbTiO_{3}-based solid solutions with giant piezoelectric effect. As such, our results not only identify the evolving atomistic disorder in a perovskite-based ferroelectric system, but also suggest that polarization instability can serve as a generic fingerprint for phase transitions as well as for better understanding structure-property relationships in PbTiO_{3}-based ferroelectric solid solutions.

The formation of a spin glass generally requires that magnetic exchange interactions are both frustrated and disordered. Consequently, the origin of spin-glass behavior in Y_{2}Mo_{2}O_{7}-in which magnetic Mo^{4+} ions occupy a frustrated pyrochlore lattice with minimal compositional disorder-has been a longstanding question. Here, we use neutron and x-ray pair-distribution function (PDF) analysis to develop a disorder model that resolves apparent incompatibilities between previously reported PDF, extended x-ray-absorption fine structure spectroscopy, and NMR studies, and provides a new and physical explanation of the exchange disorder responsible for spin-glass formation. We show that Mo^{4+} ions displace according to a local "two-in-two-out" rule on each Mo_{4} tetrahedron, driven by orbital dimerization of Jahn-Teller active Mo^{4+} ions. Long-range orbital order is prevented by the macroscopic degeneracy of dimer coverings permitted by the pyrochlore lattice. Cooperative O^{2-} displacements yield a distribution of Mo-O-Mo angles, which in turn introduces disorder into magnetic interactions. Our study demonstrates experimentally how frustration of atomic displacements can assume the role of compositional disorder in driving a spin-glass transition.

By using a symmetry motivated basis to evaluate local distortions against pair distribution function data, we show without prior bias, that the off-center Ti displacements in the archetypal ferroelectric BaTiO_{3} are zone centered and rhombohedral-like across its known ferroelectric and paraelectric phases. We construct a simple Monte Carlo model that captures our main experimental findings and demonstrate how the rich crystallographic phase diagram of BaTiO_{3} emerges from correlations of local symmetry-breaking distortions alone. Our results strongly support the order-disorder picture for these phase transitions, but can also be reconciled with the soft-mode theory of BaTiO_{3} that is supported by some spectroscopic techniques.

The structural and magnetic properties of deuterated herbertsmithite have been studied by means of neutron powder diffraction and magnetic susceptibility measurements in a wide range of temperatures and pressures. The experimental data demonstrate that a phase transition from the quantum-disordered spin-liquid phase to the long-range ordered antiferromagnetic phase with the Néel temperature T(N)=6  K is induced at P=2.5  GPa. The observed decrease of T(N) upon compression correlates with the anomalies in pressure behavior of Cu-O bond length and Cu-O-Cu bond angles. The reasons for the observed spin-freezing transition are discussed within the framework of the available theoretical models and the recent observation of the field-induced spin freezing.

ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300 degrees C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400 degrees C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

ZrW2O8 undergoes a high-pressure amorphization transition above 1.5 GPa to a phase which is recoverable to ambient conditions. Reverse Monte Carlo modeling of neutron and x-ray total scattering data from ZrW2O8 recovered from approximately 4 GPa shows that the large increase in density on pressurizing ZrW2O8 is accommodated within the structure by increased bonding between the WO4 tetrahedra. This increases the tungsten coordination; changes to the ZrO6 octahedral environment are not required. This densified crystal-based model, which contains significant local disorder within a distorted periodic structure, is also in reasonable agreement with x-ray and neutron total scattering data measured in situ at high pressure.

Total neutron scattering data from a powdered sample of MnO collected at 10 K have been analyzed using the reverse Monte Carlo method to refine the nuclear and magnetic structure. The results give the first unambiguous assignment of the average magnetic structure. The magnetic moments are aligned ferromagnetically within (111) sheets with the magnetization vectors of alternate sheets along axes parallel and antiparallel to the <112> directions, albeit with a small modulated out-of-plane component. Small displacements of Mn and O (modulated with the same periodicity) accompany the magnetic ordering and both atomic and magnetic structures may be described in the monoclinic space group C2.

The local structure of the low-temperature ordered phase of the negative thermal expansion (NTE) material has been investigated by reverse Monte Carlo (RMC) modeling of neutron total scattering data. We obtain, for the first time, quantitative measurements of the extent to which the and polyhedra move as rigid units, and we show that these values are consistent with the predictions of rigid unit mode theory. We suggest that rigid unit modes are associated with the NTE. Our results do not support a recent interpretation of x-ray-absorption fine structure spectroscopy data in terms of a larger rigid structural component involving the Zr-O-W linkage.

We describe a model-independent approach for the extraction of detailed lattice dynamics information from neutron powder diffraction data, based on a statistical analysis of atomistic configurations generated using reverse Monte Carlo structural refinement. Phonon dispersion curves for MgO extracted in this way are shown to reproduce many of the important features found in those determined independently using neutron triple-axis spectroscopy. By means of molecular dynamics simulations, we quantify the extent to which the diffraction data are sensitive to lattice dynamics in this system.