Design of crystal-like aperiodic solids with selective disorder--phonon coupling

Functional materials design normally focuses on structurally-ordered systems because disorder is considered detrimental to many important physical properties. Here we challenge this paradigm by showing that particular types of strongly-correlated disorder can give rise to useful characteristics that are inaccessible to ordered states. A judicious combination of low-symmetry building unit and high-symmetry topological template leads to aperiodic "procrystalline" solids that harbour this type of topological disorder. We identify key classes of procrystalline states together with their characteristic diffraction behaviour, and establish a variety of mappings onto known and target materials. Crucially, the strongly-correlated disorder we consider is associated with specific sets of modulation periodicities distributed throughout the Brillouin zone. Lattice dynamical calculations reveal selective disorder-phonon coupling to lattice vibrations characterised by these same periodicities. The principal effect on the phonon spectrum is to bring about dispersion in energy rather than wave-vector, as in the poorly-understood "waterfall" effect observed in relaxor ferroelectrics. This property of procrystalline solids suggests a mechanism by which strongly-correlated topological disorder might allow new and useful functionalities, including independently-optimised thermal and electronic transport behaviour as required for high-performance thermoelectrics.Comment: 4 figure

Bifurcated polarization rotation in bismuth-based piezoelectrics

ABO3 perovskite-type solid solutions display a large variety of structural and physical properties, which can be tuned by chemical composition or external parameters such as temperature, pressure, strain, electric, or magnetic fields. Some solid solutions show remarkably enhanced physical properties including colossal magnetoresistance or giant piezoelectricity. It has been recognized that structural distortions, competing on the local level, are key to understanding and tuning these remarkable properties, yet, it remains a challenge to experimentally observe such local structural details. Here, from neutron pair-distribution analysis, a temperature-dependent 3D atomic-level model of the lead-free piezoelectric perovskite Na0.5Bi0.5TiO3 (NBT) is reported. The statistical analysis of this model shows how local distortions compete, how this competition develops with temperature, and, in particular, how different polar displacements of Bi3+ cations coexist as a bifurcated polarization, highlighting the interest of Bi-based materials in the search for new lead-free piezoelectrics

Magellan/M2FS Spectroscopy of Galaxy Clusters: Stellar Population Model and Application to Abell 267

We report the results of a pilot program to use the Magellan/M2FS spectrograph to survey the galactic populations and internal kinematics of galaxy clusters. For this initial study, we present spectroscopic measurements for $223$ quiescent galaxies observed along the line of sight to the galaxy cluster Abell 267 ($z\sim0.23$). We develop a Bayesian method for modeling the integrated light from each galaxy as a simple stellar population, with free parameters that specify redshift ($v_\mathrm{los}/c$) and characteristic age, metallicity ($\mathrm{[Fe/H]}$), alpha-abundance ($[\alpha/\mathrm{Fe}]$), and internal velocity dispersion ($\sigma_\mathrm{int}$) for individual galaxies. Parameter estimates derived from our 1.5-hour observation of A267 have median random errors of $\sigma_{v_\mathrm{los}}=20\ \mathrm{km\ s^{-1}}$, $\sigma_{\mathrm{Age}}=1.2\ \mathrm{Gyr}$, $\sigma_{\mathrm{[Fe/H]}}=0.11\ \mathrm{dex}$,$\sigma_{[\alpha/\mathrm{Fe}]}=0.07\ \mathrm{dex}$, and$\sigma_{\sigma_\mathrm{int}}=20\ \mathrm{km\ s^{-1}}$. In a companion paper, we use these results to model the structure and internal kinematics of A267.Comment: 16 pages, 11 figures, accepted for publication in The Astronomical Journa

Structure–property insights into nanostructured electrodes for Li-ion batteries from local structural and diffusional probes

Microwave heating presents a faster, lower energy synthetic methodology for the realization of functional materials. Here, we demonstrate for the first time that employing this method also leads to a decrease in the occurrence of defects in olivine structured LiFe1−xMnxPO4. For example, the presence of antisite defects in this structure precludes Li+ diffusion along the b-axis leading to a significant decrease in reversible capacities. Total scattering measurements, in combination with Li+ diffusion studies using muon spin relaxation (μ+SR) spectroscopy, reveal that this synthetic method generates fewer defects in the nanostructures compared to traditional solvothermal routes. Our interest in developing these routes to mixed-metal phosphate LiFe1−xMnxPO4 olivines is due to the higher Mn2+/3+ redox potential in comparison to the Fe2+/3+ pair. Here, single-phase LiFe1−xMnxPO4 (x = 0, 0.25, 0.5, 0.75 and 1) olivines have been prepared following a microwave-assisted approach which allows for up to 4 times faster reaction times compared to traditional solvothermal methods. Interestingly, the resulting particle morphology is dependent on the Mn content. We also examine their electrochemical performance as active electrodes in Li-ion batteries. These results present microwave routes as highly attractive for reproducible, gram-scale syntheses of high quality nanostructured electrodes which display close to theoretical capacity for the full iron phase