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NASA NTRS1993

Optimal cube-connected cube multiprocessors

Many CFD (computational fluid dynamics) and other scientific applications can be partitioned into subproblems. However, in general the partitioned subproblems are very large. They demand high performance computing power themselves, and the solutions of the subproblems have to be combined at each time step. The cube-connect cube (CCCube) architecture is studied. The CCCube architecture is an extended hypercube structure with each node represented as a cube. It requires fewer physical links between nodes than the hypercube, and provides the same communication support as the hypercube does on many applications. The reduced physical links can be used to enhance the bandwidth of the remaining links and, therefore, enhance the overall performance. The concept and the method to obtain optimal CCCubes, which are the CCCubes with a minimum number of links under a given total number of nodes, are proposed. The superiority of optimal CCCubes over standard hypercubes was also shown in terms of the link usage in the embedding of a binomial tree. A useful computation structure based on a semi-binomial tree for divide-and-conquer type of parallel algorithms was identified. It was shown that this structure can be implemented in optimal CCCubes without performance degradation compared with regular hypercubes. The result presented should provide a useful approach to design of scientific parallel computers.

Sun, Xian-He↗

NASA NTRS1994

Software for continuum modeling of controls-structures interactions

It is clear that computer software is needed to assist in the generation of the equations of motion for complex, flexible spacecraft. Daniel Poelaert of ESTEC has developed the software DISTEL with which he has modeled the structural dynamics for different satellites. He is interested in expanding the capabilities of DISTEL to include structural damping and control systems. Unfortunately, the software has not been released. The author has developed similar software, PDEMOD, which has been used to model the Spacecraft control Laboratory Experiment (SCOLE), the Solar Array Flight Experiment (SAFE), the Mini-MAST truss, and the LACE satellite. PDEMOD has been used also for optimal parameter estimation and integrated control-structures design. PDEMOD is also being extended to include structural damping and control systems which are imbedded into the same equations for the structural dynamics. This paper will address the formulation of the equations for the structural dynamics of spacecraft structures which are constructed of a 3-dimensional arrangement of rigid bodies and flexible beam elements. Control system dynamics are imbedded into the same equations so that model order reduction approximations are not necessary. The input data consists of the physical data of the elements and the topological information describing how the elements are connected. PDEMOD accomplishes the following: (1) automatically assembles the equations of motion for the entire structural model; (2) calculates the modal frequencies; (3) calculates the mode shapes; (4) generates perspective views of the mode shapes; and (5) forms selected transfer functions. The software PDEMOD continues to be developed to provide additional features to assist in analyzing and synthesizing control and structural systems for flexible spacecraft.

Taylor, Lawrence W., Jr.↗

NASA NTRS1995

Analysis of LDEF experiment AO187-2 chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry

#Experiment AO187-2, that was flown on board the Long Duration Exposure Facility(LDEF), was designed to measure the chemical and isotopic compositions of interplanetary dust impinging on the spacecraft from outer space. Information on the nature and composition of orbital debris was also anticipated. The spacecraft maintained a constant orientation with respect to its velocity vector thereby defining leading and trailing edges that faced respectively into and away from the direction of motion. Arrays of individual capture cells each 80.8 sq cm in size and totaling 237 in number were exposed on both the leading and trailing edges of LDEF. Each cell consisted of a pure Ge target surface slightly separated from a thin (2.5 micrometers) metallized plastic 'entrance foil.' The basic concept was that incoming projectiles would penetrate the foil, strike the Ge target plate at high velocity producing a vapor-liquid cloud that would re-deposit material on the underside of the plastic foil. This material would then be analyzed using the sensitive surface analysis technique of Secondary Ion Mass Spectrometry (SIMS). In practice, most of the plastic entrance foils failed during the extended period of orbital exposure probably due to a combination of UV embrittlement, large densities of impact events and (for the leading edge) the effects of atomic oxygen erosion in orbit. However the foils failed gradually and most remained in place on the capture cells for a significant fraction of the duration of the flight . Because most of the impactors were small (less than 10 micrometers) they were heated and dispersed in traversing the entrance foils producing clouds of molten droplets and vapor that produced easily identifiable 'extended impacts' on the Ge target plates. Fortunately, it proved possible to make ion probe measurements of projectile compositions from material deposited on the Ge in the extended impact structures.

Zinner, Ernst↗

NASA NTRS1998

The Magnetic Roots of Enhanced Coronal Heating

Building a description of the sites of enhanced heating in the solar atmosphere has been a primary interest of the solar group at MSFC. For locations within and between active regions, as well as in the quiet Sun, this work shows that extended magnetic structures are heated from active compact magnetic structures at their feet. This talk will review what we have learned about the magnetic characteristics of these active footpoint sites, and the relationships of the intensity variations in the low-lying and higher structures, in the context of current theories and observations of magnetic reconnection and jets. One puzzling result is the poor correlation of intensity variations in the low and high loops.

Porter, J. G.↗

NASA NTRS2007

Eta Carinae: Viewed from Multiple Vantage Points

The central source of Eta Carinae and its ejecta is a massive binary system buried within a massive interacting wind structure which envelops the two stars. However the hot, less massive companion blows a small cavity in the very massive primary wind, plus ionizes a portion of the massive wind just beyond the wind-wind boundary. We gain insight on this complex structure by examining the spatially-resolved Space Telescope Imaging Spectrograph (STIS) spectra of the central source (0.1") with the wind structure which extends out to nearly an arcsecond (2300AU) and the wind-blown boundaries, plus the ejecta of the Little Homunculus. Moreover, the spatially resolved Very Large Telescope/UltraViolet Echelle Spectrograph (VLT/UVES) stellar spectrum (one arcsecond) and spatially sampled spectra across the foreground lobe of the Homunculus provide us vantage points from different angles relative to line of sight. Examples of wind line profiles of Fe II, and the.highly excited [Fe III], [Ne III], [Ar III] and [S III)], plus other lines will be presented.

Gull, Theodore↗

NASA NTRS2011

Damage Characterization Using the Extended Finite Element Method for Structural Health Management

The development of validated multidisciplinary Integrated Vehicle Health Management (IVHM) tools, technologies, and techniques to enable detection, diagnosis, prognosis, and mitigation in the presence of adverse conditions during flight will provide effective solutions to deal with safety related challenges facing next generation aircraft. The adverse conditions include loss of control caused by environmental factors, actuator and sensor faults or failures, and damage conditions. A major concern in these structures is the growth of undetected damage/cracks due to fatigue and low velocity foreign impact that can reach a critical size during flight, resulting in loss of control of the aircraft. Hence, development of efficient methodologies to determine the presence, location, and severity of damage/cracks in critical structural components is highly important in developing efficient structural health management systems.

Krishnamurthy, Thiagarajan↗

NASA NTRS2011

Multiclass Continuous Correspondence Learning

We extend the Structural Correspondence Learning (SCL) domain adaptation algorithm of Blitzer er al. to the realm of continuous signals. Given a set of labeled examples belonging to a 'source' domain, we select a set of unlabeled examples in a related 'target' domain that play similar roles in both domains. Using these 'pivot samples, we map both domains into a common feature space, allowing us to adapt a classifier trained on source examples to classify target examples. We show that when between-class distances are relatively preserved across domains, we can automatically select target pivots to bring the domains into correspondence.

correspondence learning↗

NASA NTRS2017

Tidal Prediction

Tides are the most predictable of oceanographic phenomena, due both to the simplicity and predictability of the astronomical forcing and to the near linearity of the ocean's dynamical response. In the classical and simplest scenario, tidal prediction is based on harmonic analysis of past measurements at a fixed location. Limits to predictability arise because isolated astronomical spectral lines are broadened into "cusps" of incoherent energy, for example through interactions with non-tidal flows. Tidal prediction at locations without past measurements has historically been a major challenge, but, owing to near-global observations of modern satellite altimeters, the empirical harmonic approach now yields reasonably accurate predictions throughout most of the open ocean. Advances in numerical modeling and data assimilation allow these predictions to be refined (especially in shallow seas where observations remain insufficient to directly constrain tidal wave structure) and extended to include tidal currents. We review recent progress in the development of global and regional-scale tidal prediction capabilities, summarize accuracy of available charts, and briefly consider outstanding issues. Satellite altimetry has also helped unravel the global tidal energy budget and has clarified the role of internal tides as a sink of tidal energy. We summarize these results, and then turn to the challenging problem of predicting internal tides. To the extent that low modes remain coherent with the surface tide, elevations can be directly mapped. We review current efforts in this direction, which are already producing charts with predictive capability. However, internal tides (especially higher modes) interact much more strongly with lower-frequency ocean flows, so a significant fraction of this tidal signal is intermittent and incoherent. We close with a brief review of ongoing efforts to model global tides in combination with wind-forced ocean motions.

Harmonic Constants↗

NASA NTRS2019

The Distribution, Composition, and Particle Properties of Mars Mesospheric Aerosols: an Analysis of CRISM Visible/near-IR Limb Spectra with Context from Near-Coincident MCS and MARCI Observations

The Compact Reconnaissance Imaging Spectral Mapper (CRISM) onboard the Mars Reconnaissance Orbiter (MRO) obtains pole-to-pole observations (i.e., full MRO orbits) of vertical profiles for visible/near-IR spectra (λ=0.4–4.0 μm), which are ideally suited to identifying the composition and particle sizes of Mars ice and dust aerosols over 50–100 km altitudes in the Mars mesosphere. Within the coverage limitations of the CRISM limb data set, a distinct compositional dichotomy is found in Mars mesospheric ice aerosols. CO2 ice clouds appear during the aphelion period of Mars orbit (Solar Longitudes, Ls∼0–160°) at low latitudes (∼20S–10N) over specific longitude regions (Meridiani, Valles Marineris) and at typical altitudes of 55–75 km. Apart from faint water ice hazes below 55 km, mesospheric H2O ice clouds are primarily restricted to the perihelion orbital range (Ls∼160 – 350°) at northern and southern mid-to-low latitudes with less apparent longitudinal dependences. Mars mesospheric CO2 clouds are presented in CRISM spectra with a surprisingly large range of particle sizes (cross section weighted radii, Reff=0.3 to 2.2 μm). The smaller particle sizes (Reff ≤1 μm) appear concentrated near the spatial (latitude and altitude) boundaries of their global occurrences. CRISM spectra of mesospheric CO2 clouds also show evidence of iridescence, indicating very narrow particle size distributions (effective variance, Veff∼0.03) and so very abrupt CO2 cloud nucleation. Furthermore, these clouds are sometimes accompanied by altitude coincident peaks in 1.27 μm O2 dayglow, which indicates very dry, cold regions of formation. Mesospheric water ice clouds generally exhibit small particle sizes (Reff=0.1–0.3 μm), although larger particle sizes (Reff=0.4–0.7 μm) appear infrequently. On average, water ice cloud particle sizes decrease with altitude over 50–80 km in the perihelion mesosphere. Water ice mass appears similar in clouds over a large range of observed cloud particle sizes, with particle number densities increasing to ∼10 cm−3 for Reff=0.2 μm. Near coincident Mars Climate Sounder (MCS) temperature and aerosol profile measurements for a subset of CRISM mesospheric aerosol measurements indicate near saturation (H2O and CO2) conditions for ice clouds and distinct mesospheric temperature increases associated with mesospheric dust loading. Dayside (3 pm) mesospheric CO2 clouds with larger particle sizes (Reff ≥0.5 μm) scatter surface infrared emission in MCS limb infrared radiances, as well as solar irradiance in the MCS solar band channel. Scattering of surface infrared emission is most strikingly presented in nighttime (3 am) MCS observations at 55–60 km altitudes, indicating extensive mesospheric nighttime CO2 clouds with considerably larger particle sizes (Reff∼7 μm). Mesospheric CO2 ice clouds present cirrus-like waveforms over extensive latitude and longitude regions (10°×10°), as revealed in coincident Mars Color Imager (MARCI) nadir imaging. Solar tides, gravity waves, and the large orbital variation of the extended thermal structure of the Mars atmosphere influence all of these behaviors. Mesospheric dust aerosols appear infrequently over the non-global (planet encircling) dust storm era of the CRISM limb data set (2009–2016), and exhibit smaller particle sizes (Reff=0.2–0.7 μm) relative to dust in the lower atmosphere. One isolated case of an aphelion (Ls=96°) mesospheric dust layer with large dust particle sizes (Reff ∼2 μm) over Syria Planum may reflect high altitude, non-local transport of dust over elevated regions.

Clancy, Todd R.↗

NASA NTRS1992

The Starburst-AGN Connection: A Sensitive VLBI Survey of Luminous IRAS Galaxies

Results of an 18 cm VLBI survey of 31 luminous (L_(fir) greater than 10^(11.25)L dot circle),radio-compact (theta less than approximately 0."25) infrared galaxies are presented. Over half thesample galaxies show high-brightness temperature emission, with T_b greater than 10^5K andstructure on scales of 5 - 150 mas. The median VLBI core power for detected sources is log P_(core)= 22.0(WHz^(-1)0, and the ratio of core to total 1.6 GHz flux density less than S_(core)/S_(total)greater than = 0.12. The limits for non- detected sources are similar, consistent with a picture inwhich all the galaxies have compact cores at a level of a few percent of the total radio flux density. Characteristics of the extended radio structure, infrared properties and optical excitation are not goodindicators of the detectability of VLBI-scale emission. Structural information and energeticconsiderations rule out a single supernova interpretation of the compact emission in these galaxies,though we cannot exclude the possibility of several simultaneous extraordinarily luminous radiosupernovae within the central few hundred pc^3. Our results instead favor the presence of an AGNobscured by starburst-related dust.

Lonsdale, Carol J.↗

NASA NTRS2019

The distribution, composition, and particle properties of Mars mesospheric aerosols: An analysis of CRISM visible/near-IR limb spectra with context from near-coincident MCS and MARCI observations

The Compact Reconnaissance Imaging Spectral Mapper (CRISM) onboard the Mars Reconnaissance Orbiter (MRO) obtains pole-to-pole observations (i.e., full MRO orbits) of vertical profiles for visible/near-IR spectra (λ= 0.4–4.0 μm), which are ideally suited to identifying the composition and particle sizes of Mars ice and dust aerosols over 50–100 km altitudes in the Mars mesosphere. Within the coverage limitations of the CRISM limb data set, a distinct compositional dichotomy is found in Mars mesospheric ice aerosols. CO2 ice clouds appear during the aphelion period of Mars orbit (Solar Longitudes, L(s )∼ 0–160°) at low latitudes (∼20S–10N) over specific longitude regions (Meridiani, Valles Marineris) and at typical altitudes of 55–75 km. Apart from faint water ice hazes below 55 km, mesospheric H2O ice clouds are primarily restricted to the perihelion orbital range (L(s)∼160 – 350°) at northern and southern mid-to-low latitudes with less apparent longitudinal dependences. Mars mesospheric CO2 clouds are presented in CRISM spectra with a surprisingly large range of particle sizes (cross section weighted radii, R(eff) = 0.3 to 2.2 μm). The smaller particle sizes (R(eff) ≤1 μm) appear concentrated near the spatial (latitude and altitude) boundaries of their global occurrences. CRISM spectra of mesospheric CO2 clouds also show evidence of iridescence, indicating very narrow particle size distributions (effective variance, V(eff) ∼ 0.03) and so very abrupt CO2 cloud nucleation. Furthermore, these clouds are sometimes accompanied by altitude coincident peaks in 1.27 μm O2 dayglow, which indicates very dry, cold regions of formation. Mesospheric water ice clouds generally exhibit small particle sizes (R(eff) = 0.1–0.3 μm), although larger particle sizes (R(eff) = 0.4–0.7 μm) appear infrequently. On average, water ice cloud particle sizes decrease with altitude over 50–80 km in the perihelion mesosphere. Water ice mass appears similar in clouds over a large range of observed cloud particle sizes, with particle number densities increasing to ∼10 per cu. cm for R(eff) = 0.2 μm. Near coincident Mars Climate Sounder (MCS) temperature and aerosol profile measurements for a subset of CRISM mesospheric aerosol measurements indicate near saturation (H2O and CO2) conditions for ice clouds and distinct mesospheric temperature increases associated with mesospheric dust loading. Dayside (3 pm) mesospheric CO2 clouds with larger particle sizes (R(eff) ≥0.5 μm) scatter surface infrared emission in MCS limb infrared radiances, as well as solar irradiance in the MCS solar band channel. Scattering of surface infrared emission is most strikingly presented in nighttime (3 am) MCS observations at 55–60 km altitudes, indicating extensive mesospheric nighttime CO2 clouds with considerably larger particle sizes (R(eff)∼7 μm). Mesospheric CO2 ice clouds present cirrus-like waveforms over extensive latitude and longitude regions (10°×10°), as revealed in coincident Mars Color Imager (MARCI) nadir imaging. Solar tides, gravity waves, and the large orbital variation of the extended thermal structure of the Mars atmosphere influence all of these behaviors. Mesospheric dust aerosols appear infrequently over the non-global (planet encircling) dust storm era of the CRISM limb data set (2009–2016), and exhibit smaller particle sizes (R(eff) = 0.2–0.7 μm) relative to dust in the lower atmosphere. One isolated case of an aphelion (L(s) = 96°) mesospheric dust layer with large dust particle sizes (R(eff) ∼2 μm) over Syria Planum may reflect high altitude, non-local transport of dust over elevated regions.

R. Todd Clancy↗

NASA NTRS2021

Simultaneous UV Images and High-Latitude Particle and Field Measurements During an Auroral Dawn Storm at Jupiter

We present multi-instrument Juno observations on day-of-year 86, 2017 that link particles and fields in Jupiter's polar magnetosphere to transient UV emissions in Jupiter's northern auroral region known as dawn storms. Juno ranged from 42°N to 51°N in magnetic latitude and 5.8–7.8 Jovian radii (1 RJ = 71,492 km) during this period. These dawn storm emissions consisted of two separate, elongated structures which extended into the nightside, rotated with the planet, had enhanced brightness (up to at least 1.4 megaRayleigh) and high color ratios. The color ratio is a proxy for the atmospheric penetration depth and therefore the energy of the electrons that produce the UV emissions. Juno observed electrons and ions on magnetic field lines mapping to these emissions. The electrons were primarily field-aligned, bidirectional, and, at times, exhibited sudden intensity decreases below ∼10 keV coincident with intensity enhancements up to energies of ∼1,000 keV, consistent with the high color ratio observations. The more energetic electron distributions had characteristic energies of ∼160–280 keV and downward energy fluxes (∼70–135 mW m−2) that were a significant fraction needed to produce the UV emissions for this event. Magnetic field perturbations up to ∼0.7% of the local magnetic field showing evidence of upward and downward field-aligned currents, whistler mode waves, and broadband kilometric radio emissions were also observed along Juno's trajectory during this time frame. These high-latitude observations show similarities to those in the equatorial magnetosphere associated with dynamics processes such as interchange events, plasma injections, and/or tail reconnection.

R. W. Ebert↗

NASA NTRS2022

Ultraviolet Spectropolarimetry Conservative and Nonconservative Mass Transfer in OB Interacting Binaries

The current consensus is that at least half of the OB stars are formed in binary or multiple star systems. The evolution of OB stars is greatly influenced by whether the stars begin as close binaries, and the evolution of the binary systems depend on whether the mass transfer is conservative or nonconservative. FUV/NUV spectropolarimetry is poised to answer the latter question. This paper discusses how the Polstar spectropolarimetry mission can characterize the degree of nonconservative mass transfer that occurs at various stages of binary evolution, from the initial mass reversal to the late Algol phase, and quantify its amount. The proposed instrument combines spectroscopic and polarimetric capabilities, where the spectroscopy can resolve Doppler shifts in UV resonance lines with 10 km/s precision, and polarimetry can resolve linear polarization with 10 −3 precision or better. The spectroscopy will identify absorption by mass streams and other plasmas seen in projection against the stellar disk as a function of orbital phase, as well as scattering from extended splash structures, including jets. The polarimetry tracks the light coming from material not seen against the stellar disk, allowing the geometry of the scattering to be tracked, resolving ambiguities left by the spectroscopy and light-curve information. For example, nonconservative mass streams ejected in the polar direction will produce polarization of the opposite sign from conservative transfer accreting in the orbital plane. Time domain coverage over a range of phases of the binary orbit are well supported by the Polstar observing strategy. Special attention will be given to the epochs of enhanced systemic mass loss that have been identified from IUE observations (pre-mass reversal and tangential gas stream impact). We show how the history of systemic mass and angular momentum loss/gain episodes can be inferred via ensemble evolution through the r–q diagram. Combining the above elements will significantly improve our understanding of the mass transfer process and the amount of mass that can escape from the system, an important channel for changing the final mass and ultimate supernova of a large number of massive stars found in binaries at close enough separation to undergo interaction.

Geraldine J. Peters↗

NASA NTRS2024

Pulsar-wind-nebula-powered Galactice center X-ray filament G0.13-0.11

We report the discovery of X-ray polarization from the X-ray-bright filament G0.13−0.11 in the Galactic center (GC) region. This filament features a bright, hard X-ray source that is most plausibly a pulsar wind nebula (PWN) and an extended and structured diffuse component. Combining the polarization signal from IXPE with the imaging/spectroscopic data fromChandra, we find that X-ray emission of G0.13−0.11 is highly polarized PD=57(±18)% in the 3−6 keV band, while the polarization angle is PA=21◦(±9◦). This high degree of polarization proves the synchrotron origin of the X-ray emission from G0.13−0.11. In turn, the measured polarization angle implies that the X-ray emission is polarized approximately perpendicular to a sequence of nonthermal radio filaments that may be part of the GC Radio Arc. The magnetic field on the order of 100μGappears to be preferentially ordered along the filaments. The above field strength is the fiducial value that makes our model self-consistent, while the other conclusions are largely model independent

magnetic fields↗

DOE OSTI2021

Spin texture induced by non-magnetic doping and spin dynamics in 2D triangular lattice antiferromagnet h -Y(Mn,Al)O 3

Novel effects induced by nonmagnetic impurities in frustrated magnets and quantum spin liquid represent a highly nontrivial and interesting problem. A theoretical proposal of extended modulated spin structures induced by doping of such magnets, distinct from the well-known skyrmions has attracted significant interest. Here, we demonstrate that nonmagnetic impurities can produce such extended spin structures in h-YMnO 3 , a triangular antiferromagnet with noncollinear magnetic order. Using inelastic neutron scattering (INS), we measured the full dynamical structure factor in Al-doped h-YMnO 3 and confirmed the presence of magnon damping with a clear momentum dependence. Our theoretical calculations can reproduce the key features of the INS data, supporting the formation of the proposed spin textures. As such, our study provides the first experimental confirmation of the impurity-induced spin textures. It offers new insights and understanding of the impurity effects in a broad class of noncollinear magnetic systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Measurements of K-edge and L-edge extended x-ray absorption fine structure at the national ignition facility (invited)

High-energy-density laser facilities and advances in dynamic compression techniques have expanded access to material states in the Terapascal regime relevant to inertial confinement fusion, planetary science, and geophysics. However, experimentally determining the material temperature in these extreme conditions has remained a difficult challenge. Extended X-ray Absorption Fine Structure (EXAFS), referring to the modulations in x-ray absorption above an absorption edge from photoelectrons’ interactions with neighboring atoms, has proven to be a versatile and robust technique for probing material temperature and density for mid-to-high Z elements under dynamic compression. The current platform at the National Ignition Facility has developed six configurations for EXAFS measurements between 7 and 18 keV for different absorption edges (Fe K, Co K, Cu K, Ta L3, Pb L3, and Zr K) using a curved-crystal spectrometer and a bright, continuum foil x-ray source. Here, in this work, we describe the platform geometry, x-ray source performance, spectrometer resolution and throughput, design considerations, and data in ambient and dynamic-compression conditions.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Local ordering in Ge/Ge–Sn semiconductor alloy core/shell nanowires revealed by extended x-ray absorption fine structure (EXAFS)

Short-range atomic order in semiconductor alloys is a relatively unexplored topic that may promote design of new materials with unexpected properties. Here, local atomic ordering is investigated in Ge–Sn alloys, a group-IV system that is attractive for its enhanced optoelectronic properties achievable via a direct gap for Sn concentrations exceeding ≈10 at. %. The substantial misfit strain imposed on Ge–Sn thin films during growth on bulk Si or Ge substrates can induce defect formation; however, misfit strain can be accommodated by growing Ge–Sn alloy films on Ge nanowires, which effectively act as elastically compliant substrates. In this work, Ge core/Ge 1–x Sn x (x ≈ 0.1) shell nanowires were characterized with extended x-ray absorption fine structure (EXAFS) to elucidate their local atomic environment. Simultaneous fitting of high-quality EXAFS data collected at both the Ge K-edge and the Sn K-edge reveals a large (≈ 40%) deficiency of Sn in the first coordination shell around a Sn atom relative to a random alloy, thereby providing the first direct experimental evidence of significant short-range order in this semiconductor alloy system. Furthermore, comparison of path length data from the EXAFS measurements with density functional theory simulations provides alloy atomic structures consistent with this conclusion.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Chemistry, Structure, and Function of Lone Pairs in Extended Solids

The lone pair has been a known feature of the electronic structure of molecules for over 100 years. Beginning with the pioneering work of Lewis and others that was later developed into useful guidelines for predicting molecular structure, lone pairs and their steric consequences are now taught at the very earliest stages of a chemistry education. In the crystalline solid state, lone pairs have perhaps had a less visible yet equally consequential role, with a significant impact on a range of properties and functionalities. Important properties associated with s 2 electron-derived lone pairs include their role in creating conditions favorable for ion transport, in the formation and correlation of local dipoles and the resulting polar behavior leading to ferroics and multiferroics, in increasing the refractive index of glass, in reducing the thermal conductivity of thermoelectric materials, and in breaking local symmetry permitting second-harmonic light generation.. In recent years, the role of the lone pair in developing the electronic structure of some topological quantum materials has also been recognized. While structural distortions due to lone pairs have traditionally been characterized through their crystallography, recent advances in scattering and spectroscopy have revealed the presence of local lone pair-driven distortions that do not correlate over long length scales. The role of these crystallographically “hidden” lone pairs, their detection, and their impact on properties have become a growing body of work in the literature. Hidden lone pairs are an effective argument for considering a role for lone pairs that goes beyond their being objects that occupy space in the coordination polyhedra of cations. This Account introduces the chemistry of lone pairs in extended crystalline solids, including a discussion of when they are stereochemically active, how they manifest in the structure, and how their chemistry can be tuned by the chemical environment around them. Eventually, all of these factors work in unison to help develop and tune properties of interest. Certain specific examples of structure–property relationships in materials that are driven by lone pair behavior are described here, including the potential impact of lone pairs on the optical and electronic properties of hybrid halide perovskite compounds that are relevant to their photovoltaic applications. Here, we highlight the role of lone pairs in the dielectric behavior of geometrically frustrated pyrochlores, the temperature-dependent optoelectronic behavior of halide perovskites, the polar phase transitions in lead-free ferroelectric perovskites, and the compositional insulator-to-metal transition in ruthenium pyrochlores. The theme underpinning this Account is that the lone pair can be considered to be a powerful design element for a broad range of material function.

36 MATERIALS SCIENCE↗