David Keen

Abstract:

A simple crossover from two-dimensional to three-dimensional correlated disorder of O and N atoms on a cubic lattice has been discovered within the Ba1-xSrxTaO2N series of perovskite oxynitrides. The crossover is driven by lattice expansion as x decreases, and provides a rapid increase in entropy due to a change from subextensive to extensive configurational entropy regimes.

Abstract:

The structures of chemically identical amorphous zeolitic amorphous frameworks (ZIFs), which were prepared from crystalline ZIF-4 via three different routes, are compared by refining atomistic models against their neutron and X-ray total scattering data. The diffraction data are very similar at all but the lowest values of momentum transfer and this is reflected in the ability of models with the same continuous random network topology to fit the data from each of the three amorphous ZIFs. Despite this there are differences in the detail; the relative positions of the lowest-Q peak in the Zn-Zn partial structure factors are consistent with differences in the densities of the different amorphous samples, and peaks in the ZIF-4 glass total scattering structure factors are in general broader, suggesting shorter-ranged correlations.

Abstract:

Using a combination of single-crystal neutron scattering and reverse Monte Carlo refinements, we study the magnetic structure of paramagnetic MnO at a temperature (160 K) substantially below the Curie-Weiss temperature |θ|∼550 K. The microscopic picture we develop reveals a locally ordered domain structure that persists over distances many times larger than the correlation length implied by direct analysis of the spin-correlation function. Moreover, the directional dependence of paramagnetic spin correlations in paramagnetic MnO differs in some important respects from that of its incipient ordered antiferromagnetic state. Our results demonstrate that atomistic refinement to large three-dimensional neutron-scattering datasets is a practical approach, and have implications for the understanding of paramagnetic states in weakly frustrated systems, including high-temperature superconductors.

Abstract:

Metal-organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields, covering engineering, physics, chemistry, biology and medicine. Until recently, research has focused almost entirely on crystalline structures, yet now a clear trend is emerging, shifting the emphasis onto disordered states, including 'defective by design' crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework. We combine in situ variable temperature X-ray, ex situ neutron pair distribution function experiments, and first-principles molecular dynamics simulations to study the melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.