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At least 127 records · Page 7

Berry curvature memory through electrically driven stacking transitions

In two-dimensional layered quantum materials, the interlayer stacking order determines both crystalline symmetry and quantum electronic properties such as Berry curvature, topology and electron correlation. Electrical stimuli can strongly influence quasi-particle interactions and the free energy landscape, thus making it possible to access hidden stacking orders with novel quantum properties and enabling dynamic engineering of these attributes. In this paper, we demonstrate electrically driven stacking transitions and a new type of nonvolatile memory based on Berry curvature in few-layer WTe 2 . The interplay of out-of-plane electric fields and electrostatic doping controls in-plane interlayer sliding and creates multiple polar and centrosymmetric stacking orders. In-situ nonlinear Hall transport reveals such stacking rearrangements result in a layer-parity-selective Berry curvature memory in momentum space, where the sign reversal of the Berry curvature only occurs in odd layer crystals. Our findings open an avenue towards exploring coupling between topology, electron correlations, and ferroelectricity in hidden stacking orders and demonstrate a new low energy cost, electrically-controlled topological memory in the atomically thin limit.

36 MATERIALS SCIENCE↗

Modulation of the Electronic and Vibrational Landscape in Lead Organic Chalcogenides

Metal organic chalcogenides (MOCs) are an emerging class of two-dimensional (2D) materials featuring tunable band gaps and strong light-matter interactions with great potential for optical and polaritonic applications. Lead organic chalcogenides (LOCs) stand out among MOCs for sustaining long-lived coherent optical phonons despite their distorted lattices. However, the strong electron–phonon coupling also leads to rapid charge carrier self-trapping, hindering carrier transport. Herein, we demonstrate that charge carrier self-trapping is suppressed in Se- and Te-based LOCs. Specifically, the expansive Se and Te orbitals give rise to more dispersive conduction bands and reduced electron effective masses, thereby mitigating carrier self-trapping. As a result of reduced carrier self-trapping, the Se- and Te-based LOCs exhibit enhanced band-to-band photoluminescence and improved charge transport performance. Furthermore, our results provide a synthetic route to Se- and Te-based LOC single crystals and demonstrate the potential of orbital engineering to tune their electronic and phononic properties.

Chalcogenides↗

Freestanding Ferroelectric Bubble Domains

Bubble-like domains, typically a precursor to the electrical skyrmions, arise in ultrathin complex oxide ferroelectric-dielectric-ferroelectric heterostructures epitaxially clamped with flat substrates. Here, it is reported that these specially ordered electric dipoles can also be retained in a freestanding state despite the presence of inhomogeneously distributed structural ripples. By probing local piezo and capacitive responses and using atomistic simulations, this study analyzes these ripples, sheds light on how the bubbles are stabilized in the modified electromechanical energy landscape, and discusses the difference in morphology between bubbles in freestanding and as-grown states. Furthermore, these results are anticipated to be the starting point of a new paradigm for the exploration of electric skyrmions with arbitrary boundaries and physically flexible topological orders in ferroelectric curvilinear space.

36 MATERIALS SCIENCE↗

Role of CeNiSi 2 and BaNiSn 3 Structure Types in the Emergent Magnetism of the Homologous Series Ln n +1 M n X 3 n +1 :Ce 4 Fe 3 Ge 10

The synthesis and characterization of Ce 4 Fe 3 Ge 10 , n =3 member of the homologous series Ln n+1 M n X 3n+1 (Ln = lanthanides, M = transition metal, X = tetrel), is reported. The structure can be modelled with the Cmcm space group adopting the Eu 2 Ni 2-x Sn 5 structure type, with lattice parameters of a = 4.3323 (15) Å, b = 35.507 (9) Å, and c = 4.3069 (12) Å. Members of the series for n > 2 consist of stacking of ordered (CeNiSi 2 type) and disordered (BaNiSn 3 / AuCu 3 type) subunits with the acting as a “spacer” between CeNiSi 2 subunits. Although neither CeFeGe 3 nor CeFe 0.63 Ge 2 order magnetically down to 2 K, Ce 4 Fe 3 Ge 10 is an antiferromagnet below 3.6 K. To rationalize the emergent magnetism: (i) we established the Kondo and RKKY interaction dominant regions for the Ce analogues adopting the BaNiSn 3 and CeNiSi 2 by creating an electronic landscape for each, (ii) mapped the strained subunits, due to stacking, within the series. Here, we established the CeFeGe 3 subunit within Ce 4 Fe 3 Ge 10 contracts and is located within the Kondo-interaction dominant region, while the CeFe 0.63 Ge 2 subunit expands and is in the RKKY-interaction dominant region.

36 MATERIALS SCIENCE↗

Investigation of Low-Energy Lattice Dynamics and Their Role in Superionic Na Diffusion and Ultralow Thermal Conductivity of Na 3 PSe 4 as a Solid-State Electrolyte

The atomic dynamics of Na 3 PSe 4 were investigated using a combination of neutron scattering experiments and ab initio and machine-learned molecular dynamics simulations to probe the interplay of fast ionic diffusion with atomic vibrations (phonons) of the host lattice. Our results reveal the existence of low-energy vibrational modes, simultaneously involving motions of Na + ions and framework polyanion subunits, and show that these modes become strongly overdamped in the superionic regime as they couple with the Na + hopping process. In particular, the Na+ migration energy landscape is strongly impacted by low-energy phonons derived from a soft acoustic branch of the host lattice, which modulates the diameter of the Na + diffusion channel at the bottleneck. We find that an additional factor for the enhanced Na + conductivity in Na 3 PSe 4 is the presence of Na-vacancies, which also affect the low-frequency dynamics and thermal vibration amplitudes, pointing to an interplay between Na + vacancies and host dynamics, jointly enhancing ionic diffusivity. Finally, we investigate the origin of ultralow thermal conductivities in Na 3 PSe 4 and Na 3 PS 4 using Green–Kubo simulations and find that low-energy acoustic phonon modes of the overall crystal framework provide a dominant contribution to the thermal conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The 2021 quantum materials roadmap

In recent years, the notion of ‘Quantum Materials’ has emerged as a powerful unifying concept across diverse fields of science and engineering, from condensed-matter and coldatom physics to materials science and quantum computing. Beyond traditional quantum materials such as unconventional superconductors, heavy fermions, and multiferroics, the field has significantly expanded to encompass topological quantum matter, two-dimensional materials and their van der Waals heterostructures, Moiré materials, Floquet time crystals, as well as materials and devices for quantum computation with Majorana fermions. In this Roadmap collection we aim to capture a snapshot of the most recent developments in the field, and to identify outstanding challenges and emerging opportunities. The format of the Roadmap, whereby experts in each discipline share their viewpoint and articulate their vision for quantum materials, reflects the dynamic and multifaceted nature of this research area, and is meant to encourage exchanges and discussions across traditional disciplinary boundaries. It is our hope that this collective vision will contribute to sparking new fascinating questions and activities at the intersection of materials science, condensed matter physics, device engineering, and quantum information, and to shaping a clearer landscape of quantum materials science as a new frontier of interdisciplinary scientific inquiry. We stress that this article is not meant to be a fully comprehensive review but rather an up-to-date snapshot of different areas of research on quantum materials with a minimal number of references focusing on the latest developments.

2D materials↗

Neutron scattering study of fluctuating and static spin correlations in the anisotropic spin glass Fe 2 Ti O 5

The anisotropic spin-glass transition, in which spin freezing is observed only along the c axis in pseudobrookite Fe 2 TiO 5 , has long been perplexing because the Fe 3+ moments (d 5 ) are expected to be isotropic. Recently, neutron diffraction demonstrated that surfboard-shaped antiferromagnetic nanoregions coalesce above the glass transition temperature T g ≈55K, and a model was proposed in which the freezing of the surfboard magnetization fluctuations leads to the anisotropic spin-glass state. Given this model, we have carried out high-resolution inelastic neutron scattering measurements of the spin-spin correlations to understand the temperature dependence of the intrasurfboard spin dynamics on neutron (picosecond) timescales. Here, in this paper, we report on the temperature-dependence of the spin fluctuations measured from single-crystal Fe 2 TiO 5 . Strong quasi-elastic magnetic scattering, arising from intrasurfboard correlations, is observed well above T g . The spin fluctuations possess a steep energy–wave vector relation and are indicative of strong exchange interactions, consistent with the large Curie-Weiss temperature. As the temperature approaches T g from above, a shift in spectral weight from inelastic to elastic scattering is observed. At various temperatures between 4 and 300 K, a characteristic relaxation rate of the fluctuations is determined. Despite the freezing of most of the spin correlations, an inelastic contribution remains even at base temperature, signifying the presence of fluctuating intrasurfboard spin correlations to at least T/T g ≈0.1 , consistent with an energy landscape that is a hybrid between conventional and geometrically frustrated spin glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Lattice Disorder and Oxygen Migration Pathways in Pyrochlore and Defect-Fluorite Oxides

Atomic-scale disorder plays an important role in the chemical and physical properties of oxide materials. The structural flexibility of pyrochlore-type oxides allows for crystal-chemical engineering of these properties. Compositional modification can push pyrochlore oxides toward a disordered defect-fluorite structure with anion Frenkel pair defects that facilitate oxygen migration. The local structure of the long-range average cubic defect-fluorite was recently claimed to consist of randomly arranged orthorhombic weberite-type domains. Here, we show, using low-temperature neutron total-scattering experiments, that this is not the case for Zr-rich defect-fluorites. By analyzing data from the pyrochlore/defect-fluorite Y 2 Sn 2–x Zr x O 7 series using a combination of neutron pair distribution function and big-box modelling, we have differentiated and quantified the relationship between anion sub-lattice disorder and Frenkel defects. These details directly influence the energy landscape for oxygen migration and are crucial for simulations and design of new materials with improved properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Approach for the Long-Term 30-m Land Surface Snow-Free Albedo Retrieval from Historic Landsat Surface Reflectance and MODIS-based A Priori Anisotropy Knowledge

Land surface albedo has been recognized by the Global Terrestrial Observing System (GTOS) as an essential climate variable crucial for accurate modeling and monitoring of the Earth's radiative budget. While global climate studies can leverage albedo datasets from MODIS, VIIRS, and other coarse-resolution sensors, many applications in heterogeneous environments can benefit from higher-resolution albedo products derived from Landsat. We previously developed a "MODIS-concurrent" approach for the 30-meter albedo estimation which relied on combining post-2000 Landsat data with MODIS Bidirectional Reflectance Distribution Function (BRDF) information. Here we present a "pre-MODIS era" approach to extend 30-m surface albedo generation in time back to the 1980s, through an a priori anisotropy Look-Up Table (LUT) built up from the high quality MCD43A BRDF estimates over representative homogenous regions. Each entry in the LUT reflects a unique combination of land cover, seasonality, terrain information, disturbance age and type, and Landsat optical spectral bands. An initial conceptual LUT was created for the Pacific Northwest (PNW) of the United States and provides BRDF shapes estimated from MODIS observations for undisturbed and disturbed surface types (including recovery trajectories of burned areas and non-fire disturbances). By accepting the assumption of a generally invariant BRDF shape for similar land surface structures as a priori information, spectral white-sky and black-sky albedos are derived through albedo-to-nadir reflectance ratios as a bridge between the Landsat and MODIS scale. A further narrow-to-broadband conversion based on radiative transfer simulations is adopted to produce broadband albedos at visible, near infrared, and shortwave regimes.We evaluate the accuracy of resultant Landsat albedo using available field measurements at forested AmeriFlux stations in the PNW region, and examine the consistency of the surface albedo generated by this approach respectively with that from the "concurrent" approach and the coincident MODIS operational surface albedo products. Using the tower measurements as reference, the derived Landsat 30-m snow-free shortwave broadband albedo yields an absolute accuracy of 0.02 with a root mean square error less than 0.016 and a bias of no more than 0.007. A further cross-comparison over individual scenes shows that the retrieved white sky shortwave albedo from the "pre-MODIS era" LUT approach is highly consistent (R(exp 2) = 0.988, the scene-averaged low RMSE = 0.009 and bias = −0.005) with that generated by the earlier "concurrent" approach. The Landsat albedo also exhibits more detailed landscape texture and a wider dynamic range of albedo values than the coincident 500-m MODIS operational products (MCD43A3), especially in the heterogeneous regions. Collectively, the "pre-MODIS" LUT and "concurrent" approaches provide a practical way to retrieve long-term Landsat albedo from the historic Landsat archives as far back as the 1980s, as well as the current Landsat-8 mission, and thus support investigations into the evolution of the albedo of terrestrial biomes at fine resolution.

Albedo algorithm↗

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

30 DIRECT ENERGY CONVERSION↗

Ab initio molecular dynamics free energy study of enhanced copper (II) dimerization on mineral surfaces

Understanding the adsorption of isolated metal cations from water on to mineral surfaces is critical for toxic waste retention and cleanup in the environment. Heterogeneous nucleation of metal oxyhydroxides and other minerals on material surfaces is key to crystal growth and dissolution. The link connecting these two areas, namely cation dimerization and polymerization, is far less understood. In this work we apply ab initio molecular dynamics calculations to examine the coordination structure of hydroxide-bridged Cu(II) dimers, and the free energy changes associated with Cu(II) dimerization on silica surfaces. The dimer dissociation pathway involves sequential breaking of two Cu 2+ -OH – bonds, yielding three local minima in the free energy profiles associated with 0-2 OH – bridges between the metal cations, and requires the design of a (to our knowledge) novel reaction coordinate for the simulations. Cu(II) adsorbed on silica surfaces are found to exhibit stronger tendency towards dimerization than when residing in water. Cluster-plus-implicit-solvent methods yield incorrect trends if OH – hydration is not correctly depicted. The predicted free energy landscapes are consistent with fast equilibrium times (seconds) among adsorbed structures, and favor Cu 2+ dimer formation on silica surfaces over monomer adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combining Theory and Experiment to Map the Atomic-Level Structure–Energy Pathways of Adsorbate-Mediated Phase Changes in a Cooperatively Flexible Metal–Organic Framework

An important subclass of metal–organic frameworks (MOFs) exhibits cooperative flexibility, wherein individual crystallites undergo global structural phase changes in response to external stimuli. Where cooperative flexibility results in reversible changes between crystalline states of distinct accessible porosity, these frameworks can exhibit rare yet desirable behaviors that cannot be explained by local dynamics alone. Yet, the chemical and structural origins of cooperative flexibility and how frameworks undergo these reversible phase changes at the atomic level remain poorly understood. Deliberate design for specific applications is therefore exceedingly difficult, and there is great impetus to develop a fundamental understanding of this phenomenon. Here, an effective and widely accessible computational approach is developed, which is designed to provide microscopic resolution via direct comparison to experimental data along the desorption-guided pathway. The strategy is applied to explain the desorption-induced phase change in an experimentally well-characterized framework, CdIF-13 (sod-Cd(benzimidazolate)2), where experiment alone was unable to resolve the atomistically detailed phase change landscape. Our findings reveal that the cooperative phase change pathways are adsorbate dependent with thermodynamics of intermediate structural states dictated by a nuanced interplay of ligand orientation, skeletal symmetry, and modes of surface adsorption. The results reveal that this isotropically flexible framework is “chaperoned” through a complex energy landscape by specific adsorbates, revealed by the reported computational approach with atomic-level insight and validated by experimentally determined structures. Thus, this work facilitates both understanding and future design of flexible materials for applications in gas storage, transport, delivery, and separation technologies.

03 NATURAL GAS↗

Optical pulse-induced ultrafast antiferrodistortive transition in SrTiO 3

The ultrafast dynamics of the antiferrodistortive phase transition in perovskite SrTiO 3 is monitored via time-domain Brillouin scattering. Using femtosecond optical pulses, we initiate a thermally driven tetragonal-to-cubic structural transformation and detect the crystal phase through changes in the frequency of Brillouin oscillations (BO) induced by propagating acoustic phonons. Coupling the measured BO frequency with a spatiotemporal heat diffusion model, we demonstrate that, for a sample kept in the tetragonal phase, deposition of sufficient thermal energy induces a rapid transformation of the heat-affected region to the cubic phase. The initial phase change is followed by a slower reverse cubic-to-tetragonal phase transformation occurring on a timescale of hundreds of picoseconds. Here, we attribute this ultrafast phase transformation in the perovskite to a structural resemblance between atomic displacements of the R-point soft optic mode of the cubic phase and the tetragonal phase, both characterized by anti-phase rotation of oxygen octahedra. The structural relaxation time exhibits a strong temperature dependence consistent with the prediction of the equation of motion describing collective oxygen octahedra rotation based on the energy landscape of the phenomenological Landau theory of phase transitions. Evidence of such a fast structural transition in perovskites can open up new avenues in information processing and energy storage sectors.

36 MATERIALS SCIENCE↗

Soil frost controls streamflow generation processes in headwater catchments

The relationship between snowmelt and spring streamflow is changing under warming temperatures and diminishing snowpack. At the same time, the hydrologic connectivity across catchment landscape elements, such as snowpack and surface wetlands, can play a critical role in controlling the routing of snowmelt to streams. The role of hydrologic connectivity is important in headwater regions of the continental northern latitudes, where catchments have low topographic relief and seasonally frozen ground. Nevertheless, the effects of soil frost on the sequence, timing, and magnitudes of hydrologic events that drive the movement of water from a snowpack to a stream are not fully understood. Therefore, we examine two questions: First, what is the flowpath that snow melt and precipitation from spring rain events takes to generate spring streamflow, and second, what hydrologic, climatic, or landscape variables exert the most control on the magnitude of streamflow? In this work, we use long-term hydrological records from the two reference basins at the Marcell Experimental Forest in northern Minnesota to analyze the cascading effects across precipitation, snow, water table elevation, soil frost, and streamflow in peatland-dominated headwater catchments. We identify a sequence of fill-and-spill effects across the landscape that control the timing of spring streamflow generation. Then, we use stepwise regression to show that soil frost is a key supporting predictor for both the magnitude of streamflow in the spring as it adds significantly to the predictive power of precipitation and water table elevation. Our results highlight the importance of recognizing the role of soil frost, when present, on the partitioning of snowmelt between overland runoff and water table recharge during the critical snowmelt period, as well as the later partitioning between evapotranspiration and subsurface flows.

54 ENVIRONMENTAL SCIENCES↗

Emerging Two-Dimensional Organic Semiconductor-Incorporated Perovskites–A Fascinating Family of Hybrid Electronic Materials

Halide perovskites have attracted a great amount of attention owing to their unique materials chemistry, excellent electronic properties, and low-cost manufacturing. Two-dimensional (2D) halide perovskites, originating from three-dimensional (3D) perovskite structures, are structurally more diverse and therefore create functional possibilities beyond 3D perovskites. The much less restrictive size constraints on the organic component of these hybrid materials particularly provide an exciting platform for designing unprecedented materials and functionalities at the molecular level. In this Perspective, we discuss the concept and recent development of a sub-class of 2D perovskites, namely, organic semiconductor-incorporated perovskites (OSiPs). OSiPs combine the electronic functionality of organic semiconductors with the soft and dynamic halide perovskite lattice, offering opportunities for tailoring the energy landscape, lattice and carrier dynamics, and electron/ion transport properties for various fundamental studies, as well as device applications. Specifically, we summarize recent advances in the design, synthesis, and structural analysis of OSiPs with various organic conjugated moieties as well as the application of OSiPs in photovoltaics, light-emitting devices, and transistors. As a result, challenges and further opportunities for OSiPs in molecular design, integration of novel functionality, film quality, and stability issues are addressed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Variability in Surface BRDF at Different Spatial Scales (30m-500m) Over a Mixed Agricultural Landscape as Retrieved from Airborne and Satellite Spectral Measurements

Over the past decade, the role of multiangle 1 remote sensing has been central to the development of algorithms for the retrieval of global land surface properties including models of the bidirectional reflectance distribution function (BRDF), albedo, land cover/dynamics, burned area extent, as well as other key surface biophysical quantities represented by the anisotropic reflectance characteristics of vegetation. In this study, a new retrieval strategy for fine-to-moderate resolution multiangle observations was developed, based on the operational sequence used to retrieve the Moderate Resolution Imaging Spectroradiometer (MODIS) Collection 5 reflectance and BRDF/albedo products. The algorithm makes use of a semiempirical kernel-driven bidirectional reflectance model to provide estimates of intrinsic albedo (i.e., directional-hemispherical reflectance and bihemispherical reflectance), model parameters describing the BRDF, and extensive quality assurance information. The new retrieval strategy was applied to NASA's Cloud Absorption Radiometer (CAR) data acquired during the 2007 Cloud and Land Surface Interaction Campaign (CLASIC) over the well-instrumented Atmospheric Radiation Measurement Program (ARM) Southern Great Plains (SGP) Cloud and Radiation Testbed (CART) site in Oklahoma, USA. For the case analyzed, we obtained approx.1.6 million individual surface bidirectional reflectance factor (BRF) retrievals, from nadir to 75deg off-nadir, and at spatial resolutions ranging from 3 m - 500 m. This unique dataset was used to examine the interaction of the spatial and angular 18 characteristics of a mixed agricultural landscape; and provided the basis for detailed assessments of: (1) the use of a priori knowledge in kernel-driven BRDF model inversions; (2) the interaction between surface reflectance anisotropy and instrument spatial resolution; and (3) the uncertainties that arise when sub-pixel differences in the BRDF are aggregated to a moderate resolution satellite pixel. Results offer empirical evidence concerning the influence of scale and spatial heterogeneity in kernel-driven BRDF models; providing potential new insights into the behavior and characteristics of different surface radiative properties related to land/use cover change and vegetation structure.

Roman, Miguel O.↗

Role of Pairwise Reactions on the Synthesis of Li 0.3 La 0.57 TiO 3 and the Resulting Structure–Property Correlations

The performance of single-ion conductors is highly sensitive to the material’s defect chemistry. Tuning these defects is limited for solid-state reactions as they occur at particle–particle interfaces, which provide a complex evolving energy landscape for atomic rearrangement and product formation. In this report, we investigate the (1) order of addition and (2) lithium precursor decomposition temperature and their effect on the synthesis and grain boundary conductivity of the perovskite lithium lanthanum titanium oxide (LLTO). We use an intimately mixed sol–gel, a solid-state reaction of Li precursor + La 2 O 3 + TiO 2 , and Li precursor + amorphous La 0.57 TiO x as different chemical routes to change the way in which the elements are brought together. The results show that the perovskite can accommodate a wide range of Li deficiencies (upward of 50%) while maintaining the tetragonal LLTO structure, indicating that X-ray diffraction (XRD) is insufficient to fully characterize the chemical nature of the product (i.e., Li-deficient LLTO may behave differently than stoichiometric LLTO). Variations in the relative intensities of different reflections in XRD suggest variations in the La ordering within the crystal structure between synthesis methods. Furthermore, the choice of the precursor and the order of addition of the reactants lower the time required to form a pure phase. Density functional theory calculations of the formation energy of possible reaction intermediates support the hypothesis that a greater thermodynamic driving force to form LLTO leads to a greater LLTO yield. Here, the retention of lithium is correlated with the thermal decomposition temperature of the Li precursor and the starting material mixing strategy. Taking the results together suggests that cations that share a site with Li should be mixed early to avoid ordering. Such cation ordering inhibits Li motion, leading to higher Li ion resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Variability in Surface BRDF at Different Spatial Scales (30 m-500 m) Over a Mixed Agricultural Landscape as Retrieved from Airborne and Satellite Spectral Measurements

Over the past decade, the role of multiangle remote sensing has been central to the development of algorithms for the retrieval of global land surface properties including models of the bidirectional reflectance distribution function (BRDF), albedo, land cover/dynamics, burned area extent, as well as other key surface biophysical quantities represented by the anisotropic reflectance characteristics of vegetation. In this study, a new retrieval strategy for fine-to-moderate resolution multiangle observations was developed, based on the operational sequence used to retrieve the Moderate Resolution Imaging Spectroradiometer (MODIS) Collection 5 reflectance and BRDF/albedo products. The algorithm makes use of a semiempirical kernel-driven bidirectional reflectance model to provide estimates of intrinsic albedo (i.e., directional-hemispherical reflectance and bihemispherical reflectance), model parameters describing the BRDF, and extensive quality assurance information. The new retrieval strategy was applied to NASA's Cloud Absorption Radiometer (CAR) data acquired during the 2007 Cloud and Land Surface Interaction Campaign (CLASIC) over the well-instrumented Atmospheric Radiation Measurement Program (ARM) Southern Great Plains (SGP) Cloud and Radiation Testbed (CART) site in Oklahoma, USA. For the case analyzed, we obtained approx.1.6 million individual surface bidirectional reflectance factor (BRF) retrievals, from nadir to 75 off-nadir, and at spatial resolutions ranging from 3 m - 500 m. This unique dataset was used to examine the interaction of the spatial and angular characteristics of a mixed agricultural landscape; and provided the basis for detailed assessments of: (1) the use of a priori knowledge in kernel-driven BRDF model inversions; (2) the interaction between surface reflectance anisotropy and instrument spatial resolution; and (3) the uncertain ties that arise when sub-pixel differences in the BRDF are aggregated to a moderate resolution satellite pixel. Results offer empirical evidence concerning the influence of scale and spatial heterogeneity in kernel-driven BRDF models; providing potential new insights into the behavior and characteristics of different surface radiative properties related to land/use cover change and vegetation structure.

Roman, Miguel O.↗