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At least 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Comparison of real-time and linear-response time-dependent density functional theories for molecular chromophores ranging from sparse to high densities of states

We assess the performance of real-time time-dependent density functional theory (RT-TDDFT) for the calculation of absorption spectra of 12 organic dye molecules relevant to photovoltaics and dye sensitized solar cells with 8 exchange-correlation functionals (3 traditional, 3 global hybrids, and 2 range-separated hybrids). We compare the calculations with traditional linear-response (LR) TDDFT. In addition, we demonstrate the efficacy of the RT-TDDFT approach to calculate wide absorption spectra of two large chromophores relevant to photovoltaics and molecular switches.

calculation↗
DOE OSTI2022

Tolerance Factor for Stabilizing 3D Hybrid Halide Perovskitoids Using Linear Diammonium Cations

Three-dimensional (3D) halide perovskites have attracted enormous research interest, but the choice of the A-site cations is limited by the Goldschmidt tolerance factor. In order to accommodate cations that lie outside the acceptable range of the tolerance factor, low-dimensional structures usually form. To maintain the favorable 3D connection, the links among the metal-halide octahedra need to be rearranged to fit the large cations. This can result in a departure from the proper corner-sharing perovskite architectures and lead to distinctly different perovskitoid motifs with edge- and face-sharing. In this work, we report four new 3D bromide perovskitoids incorporating linear organic diammonium cations, A'Pb 2 Br 6 (A' is a +2 cation). We propose a rule that can guide the further expansion of this class of compounds, analogous to the notion of Goldschmidt tolerance factor widely adopted for 3D AMX 3 perovskites. The fundamental building blocks in A'Pb 2 Br 6 consist of two edge-shared octahedra, which are then connected by corner-sharing to form a 3D network. Different compounds adopt different structural motifs, which can be transformed from one to another by symmetry operations. Electronic structure calculations suggest that they are direct bandgap semiconductors, with relatively large band dispersions created by octahedra connected by corner-sharing. They exhibit similar electronic band structures and dynamic lattice characteristics to the regular 3D AMX 3 perovskites. Structures with smaller Pb–Br–Pb angles and larger octahedra distortion exhibit broad photoluminescence at room temperature. Furthermore, the emerging structure–property relationships in these 3D perovskitoids set the foundation for designing and investigating these compounds for a variety of optoelectronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Cyclic versus Linear Alkylammonium Cations: Preventing Phase Transitions at Operational Temperatures in 2D Perovskites

Two-dimensional lead halide perovskites offer numerous attractive features for optoelectronics owing to their soft, deformable lattices and high degree of chemical tunability. While alteration of the metal and halide ions gives rise to significant modification of the bandgap energy, the organic spacer cations offer in-roads to tuning phase behavior and more subtle functionalities in ways that remain to be understood. Here, we study six variations of 2D perovskites changing only the organic spacer cations and demonstrate that these components intrinsically impact material response in important ways such as altering crystallographic structure, temperature-induced phase transitions, and photoluminescence emission. Two-dimensional perovskites containing commonly utilized aliphatic linear spacers, such as butylammonium, undergo phase transitions near room temperature. These transitions and temperature changes induce spacer-dependent variations in the emission spectra. Conversely, 2D perovskites comprising cyclic aliphatic spacers, such as cyclobutylammonium, are found to lack first-order phase transitions. These cyclic molecules are more sterically hindered within the crystal lattice, leading to temperature-induced contraction or expansion along certain crystallographic planes but no other significant thermal effects; additionally, they undergo changes in their emission spectra that cannot be explained by simple thermal expansion. Finally, given the similarities in the dielectric and chemical makeup of this set of six alkylammonium molecules, these results are unexpected and suggest a large structural and thermal phase space via spacer manipulation that could lead to improved 2D perovskite functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Chemical Framework to Design Linear-like Relaxors toward Capacitive Energy Storage

ABO 3 -type perovskite relaxor ferroelectrics (RFEs) have emerged as the preferred option for dielectric capacitive energy storage. However, the compositional design of RFEs with high energy density and efficiency poses significant challenges owing to the vast compositional space and the absence of general rules. Here, we present an atomic-level chemical framework that captures inherent characteristics in terms of radius and ferroelectric activity of ions. By categorizing A/B-site ions as host framework, rattling, ferroelectrically active, and blocking ions and assembling these four types of ions with specific criteria, linear-like relaxors with weak locally correlated and highly extendable unit-cell polarization vectors can be constructed. As example, we demonstrate two new compositions of Bi 0.5 K 0.5 TiO 3- based and BaTiO 3- based relaxors, showing extremely high recoverable energy densities of 17.3 and 12.1 J cm –3 , respectively, both with a high efficiency of about 90%. Further, the role of different types of ions in forming heterogeneous polar structures is identified through element-specific local structure analysis using neutron total scattering combined with reverse Monte Carlo modeling. Further, our work not only opens up new avenues toward rational compositional design of high energy storage performance lead-free RFEs but also sheds light on atomic-level manipulation of functional properties in compositionally complex ferroelectrics.

25 ENERGY STORAGE↗
DOE OSTI2026

Mechanism of O 2 /NO-Promoted Oxidative C–C Bond Cleavage in Linear Alkanes

Selective oxidation of alkanes to oxygenated products remains a fundamental challenge, particularly if the goal is to promote C−C bond cleavage while minimizing formation of CO 2 . Oxidation conditions that use O 2 and nitrogen oxides (NO x ) have been shown to be very effective in promoting radical-mediated functionalization and oxidative carbon−carbon cleavage in saturated hydrocarbon polymers, such as polyethylene. Here, we investigate the mechanism of O 2 /NO-mediated oxidation of ndecane as a prototypical linear alkane substrate. These reactions enable identification and quantification of reactive intermediates, including nitrites, nitrates, alcohols, and ketones. Under the reaction conditions, these species convert into common ketone intermediates that evolve into α-diketones and other α-functionalized ketones, which undergo further conversion into carboxylic acids. Infrared (IR) spectroscopy indicates that HDPE oxidation proceeds through similar key intermediates. Together, these findings establish a mechanistic framework for NO x -mediated alkane oxidation and provide a foundation for the development of broadly applicable oxidative transformations.

Anions↗
DOE OSTI2018

X-ray Linear Dichroism in Apatite

The recent observation in parrotfish teeth of X-ray linear dichroism motivated an in-depth investigation into this spectroscopic effect in various apatite crystals, including geologic hydroxyapatite (Ca 5 (PO 4 ) 3 OH), fluorapatite (Ca 5 (PO 4 ) 3 F), and their biogenic counterparts in human bone, mouse enamel, and in parrotfish bone, dentin, and enameloid, the equivalent of dental enamel in certain fish. These data are important because they now enable visualization of the nano- to microscale structure of apatite crystals in teeth and bone. Polarization-dependent imaging contrast (PIC) maps of lamellar bone, obtained with a new method that minimizes space-charge and charging effects, show the expected rotating apatite crystal orientations. PIC maps of mouse enamel reveal a complex arrangement of hydroxyapatite crystals perpendicular to the dentin-enamel junction, with rods arranged in a decussation pattern in inner enamel and nearly parallel to one another in outer enamel. In both inner and outer enamel crystal c-axes are not always aligned with the rod elongation direction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Toward an Understanding of Linear Scaling Relations through Energy Decomposition Analysis

The discovery of linear scaling relations has fundamentally changed the field of heterogeneous catalysis. The scaling relations have been rationalized based on the d-band theory, specifically a separation of sp and d electron contributions to adsorption energies. Within the framework of energy decomposition analysis, a full understanding of such a separation would require one to further break down the adsorption energy into distinct energy components such as electrostatics, polarization, charge transfer, and van der Waals interactions, and to examine the sp and d contributions to each of them. As a step in this direction, we analyzed the interaction energy between CH x (x = 1–4) adsorbates and fcc(100) transition metal surfaces (M = Cu, Ag, Au, Rh, and Pt), with the surfaces represented both as slabs in plane-wave density functional theory (pw-DFT) calculations and as atomic clusters in atomic-orbital basis density functional theory (ao-DFT) calculations. Through an absolutely localized molecular orbital (ALMO) based energy decomposition analysis of the ao-DFT adsorption energy, each of the interaction energy components (electrostatics, polarization, van der Waals, and charge transfer) was found to follow its own scaling relations, with an intricate interplay among these energy components yielding the overall scaling relations for the total adsorption energies. Using the recently introduced ALMO-based polarization and charge-transfer analysis schemes, we further dissected polarization into metal surface and adsorbate contributions, and charge transfer into metal → adsorbate and adsorbate → metal contributions. The contributions from the sp and d electrons of the metal to these terms were further quantified, and the dominant role of the metal d electrons was reaffirmed. These results shed light on how CHx adsorbates interact with metal surfaces and further reveal the physical origin of the scaling relations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Simplified Cartesian Basis Model for Intrapolyad Emission Intensities in the Bent-to-Linear Electronic Transition of Acetylene

The acetylene emission spectrum from the trans-bent electronically excited à state to the linear ground electronic $\tilde{X}$ state has attracted considerable attention because it grants Franck–Condon access to local bending vibrational levels of the $\tilde{X}$ state with large-amplitude motion along the acetylene ⇌ vinylidene isomerization coordinate. For emission from the ground vibrational level of the à state, there is a simplifying set of Franck–Condon propensity rules that gives rise to only one zero-order bright state per conserved vibrational polyad of the $\tilde{X}$ state. Unfortunately, when the upper level involves excitation in the highly admixed ungerade bending modes, ν 4 ' and ν 6 ' , the simplifying Franck–Condon propensity rule breaks down—as long as the usual polar basis (with v and l quantum numbers) is used to describe the degenerate bending vibrations of the $\tilde{X}$ state—and the intrapolyad intensities result from complicated interference patterns between many zero-order bright states. In this article, we show that, when the degenerate bending levels are instead treated in the Cartesian two-dimensional harmonic oscillator basis (with v x and v y quantum numbers), the propensity for only one zero-order bright state (in the Cartesian basis) is restored, and the intrapolyad intensities are simple to model, as long as corrections are made for anharmonic interactions. As a result of trans ⇌ cis isomerization in the à state, intrapolyad emission patterns from overtones of ν 4 ' and ν 6 ' evolve as quanta of trans bend (ν 3 ' ) are added, so the emission intensities are not only relevant to the ground-state acetylene ⇌ vinylidene isomerization, they are also a direct reporter of isomerization in the electronically excited state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Solid-State Structure and Crystallization in Double-Crystalline Diblock Copolymers of Linear Polyethylene and Hydrogenated Polynorbornene

Double-crystalline diblock copolymers of linear polyethylene (LPE) and hydrogenated polynorbornene (hPN) are synthesized, and their crystallization behavior and morphology are examined using small-angle (SAXS) and wide-angle X-ray scattering (WAXS). In symmetric hPN/LPE diblocks with molecular weights above 50 kg/mol, the hPN block has previously been shown to crystallize first and set the solid-state microstructure. Two-dimensional WAXS on hand-drawn fiber specimens reveals that the LPE crystals formed in confinement stack orthogonally to the hPN crystals. By adjusting total molecular weight, the order of block crystallization may be reversed, even while holding the block length ratio fixed. At a diblock molecular weight of 20 kg/mol, simultaneous time-resolved SAXS/WAXS reveals that the LPE block crystallizes first, even when LPE is the minority component, and restricts hPN to crystallize between the LPE lamellae. The relative orientation of the LPE and hPN crystals in the lower molecular weight diblocks is examined by modeling changes in the SAXS primary peak intensity on cooling two diblocks through the hPN crystal-crystal transition, where hPN densifies as it adopts a rotationally ordered crystal structure. Only a perpendicular stacking of hPN and LPE crystals consistently yields the large reduction in primary SAXS peak intensity observed for both diblocks. Thus, even though the templating block switches from hPN to LPE as the diblock molecular weight is reduced, the orthogonal stacking motif is retained for both high- and low-molecular-weight copolymers.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Robust Predictive Design of Field Measurements for Evapotranspiration Barriers Using Universal Multiple linear Regression

Surface barriers are normally installed to reduce downward water movement into contaminated zones. Specifically, evapotranspiration (ET) barriers are used to store water and release it, via ET, before it can percolate into an underlying waste zone. To assess the effectiveness of a surface barrier, we used an existing data set, model-simulated data, and a dimensionality reduction approach called universal multiple linear regression (uMLR) to optimize the required number of sensors in a 2-m thick surface barrier. To understand the usefulness of implementing predictive uMLR to accommodate multiple monitoring objectives, we compare several network designs, selected based on down-sampling of existing data, with a recommended sensor design based on model simulations performed without consideration of existing data. We further added consideration of “fuzzy” design, which allows more practical guidelines for field implementation of uMLR. We discovered that uMLR, combined with robust decision-making, provides a simple, flexible, and high-quality network design for monitoring the total water stored in a surface barrier across multiple uncertain conditions.

58 GEOSCIENCES↗
DOE OSTI2021

Does Regional Hydroclimate Change Scale Linearly With Global Warming?

Many aspects of climate change scale linearly with global warming. However, nonlinear changes are possible, especially in the context of hydroclimate, and under emissions scenarios with stabilized global temperature, as aspired to by current climate targets. In CMIP5 and 6, a progressively larger land area shows nonlinear changes as a function of global warming when considering precipitation, evaporation, and soil moisture, with the latter showing nonlinearity over ~50% of global land. Here, using ensemble simulations with the Community Earth System Model 1, in which individual forcing factors are held constant, we illustrate how nonadditive responses to anthropogenic greenhouse gases and industrial and fire-related aerosols can yield complex soil moisture changes in certain regions. This complexity contributes to uncertainty in regional soil moisture projections and suggests that the timing of, as well as model response uncertainty to, future aerosol reductions will have significant impacts on regional hydroclimate change as global temperatures stabilize.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

A Comparison of Linear Solvers for Resolving Flow in Three-Dimensional Discrete Fracture Networks

We compare various methods for resolving steady flow within three-dimensional discrete fracture networks, including direct methods, Krylov subspace methods with and without preconditioning, and multi-grid methods. We compared the performance of the methods based on compute times and scaling of the solution as a function of the number of grid nodes and log-variance of the hydraulic aperture. The methods are applied to three test cases: (a) variable density of networks with a truncated power-law distribution of fracture lengths, (b) a fixed network composed of monodisperse fracture sizes but varied permeability/aperture heterogeneity, (c) and a network based on field site in Nevada, US. We chose these cases to allow us to study the impact of the mesh size and flow properties, as well as to demonstrate our conclusions on a large-scale, realistic problem (more than 40 million mesh nodes). A direct solution using Cholesky factorization outperformed other methods for every example but was closely followed in performance by some algebraic multigrid (AMG) preconditioned Krylov subspace methods. Among the Krylov methods, conjugate gradients (CG) with an AMG preconditioner performs the best. Generally, Cholesky factorization is recommended, but CG with an AMG preconditioner may be suitable for very large problems beyond 40 million nodes where the entire linear system cannot reside in memory.

58 GEOSCIENCES↗
DOE OSTI2022

Projecting Stratocumulus Transitions on the Albedo—Cloud Fraction Relationship Reveals Linearity of Albedo to Droplet Concentrations

Satellite images show solid marine stratocumulus cloud decks (Sc) that break up over the remote oceans. The Sc breakup is initiated by precipitation and is accompanied by a strong reduction in the cloud radiative effect. Aerosol has been shown to delay the Sc breakup by postponing the onset of precipitation, however its climatic effect is uncertain. Here we introduce a new approach that allows us to re-cast currently observed cloud cover and albedo to their counterfactual cleaner world, enabling the first estimate of the radiative effect due to delayed cloud breakup. Using simple radiative approximation, the radiative forcing with respect to pre-industrial times due to delayed Sc breakup is –0.39 W m –2 . The radiative effect changes nearly linearly with aerosol due to the droplet concentration control on the cloud cover, suggesting a potentially accelerated warming if the current trend of reduction in aerosol emissions continues.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Large Ensemble Particle Filter for Spatial Climate Reconstructions Using a Linear Inverse Model

Proxy records that document the last 2000 years of climate provide evidence for the wide range of the natural climate variability from inter-annual to secular timescales not captured by the short window of recent direct observations. Assessing climate models ability to reproduce such natural variations is crucial to understand climate sensitivity and impacts of future climate change. Paleoclimate data assimilation (PDA) offers a powerful way to extend the short instrumental period by optimally combining the physics described by General Circulation Climate Models (GCMs) with information from available proxy records while taking into account their uncertainties. Here we present a new PDA approach based on a sequential importance resampling (SIR) Particle filter (PF) that uses Linear Inverse Modeling (LIM) as an emulator of several CMIP-class GCMs. We examine in a perfect-model framework the skill of the various LIMs to forecast the dynamics of the surface temperatures and provide spatial field reconstructions over the last millennium in a SIR PF. Our results show that the LIMs allow for skillful ensemble forecasts at 1-year lead-time based on GCMs dynamical knowledge with best prediction in the tropics and the North Atlantic. The PDA further provides a set of physically consistent spatial fields allowing robust uncertainty quantification related to climate models biases and proxy spatial sampling. Our results indicate that the LIM yields dynamical memory improving climate variability reconstructions and support the use of the LIM as a GCM-emulator in real reconstruction to propagate large ensembles of particles at low cost in SIR PF.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Non‐Linear Dimensionality Reduction With a Variational Encoder Decoder to Understand Convective Processes in Climate Models

Abstract Deep learning can accurately represent sub‐grid‐scale convective processes in climate models, learning from high resolution simulations. However, deep learning methods usually lack interpretability due to large internal dimensionality, resulting in reduced trustworthiness in these methods. Here, we use Variational Encoder Decoder structures (VED), a non‐linear dimensionality reduction technique, to learn and understand convective processes in an aquaplanet superparameterized climate model simulation, where deep convective processes are simulated explicitly. We show that similar to previous deep learning studies based on feed‐forward neural nets, the VED is capable of learning and accurately reproducing convective processes. In contrast to past work, we show this can be achieved by compressing the original information into only five latent nodes. As a result, the VED can be used to understand convective processes and delineate modes of convection through the exploration of its latent dimensions. A close investigation of the latent space enables the identification of different convective regimes: (a) stable conditions are clearly distinguished from deep convection with low outgoing longwave radiation and strong precipitation; (b) high optically thin cirrus‐like clouds are separated from low optically thick cumulus clouds; and (c) shallow convective processes are associated with large‐scale moisture content and surface diabatic heating. Our results demonstrate that VEDs can accurately represent convective processes in climate models, while enabling interpretability and better understanding of sub‐grid‐scale physical processes, paving the way to increasingly interpretable machine learning parameterizations with promising generative properties.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Reduced‐Order Modeling for Linearized Representations of Microphysical Process Rates

Abstract Representing cloud microphysical processes in large scale atmospheric models is challenging because many processes depend on the details of the droplet size distribution (DSD, the spectrum of droplets with different sizes in a cloud). While full or partial statistical moments of droplet size distributions are the typical variables used in bulk models, prognostic moments are limited in their ability to represent microphysical processes across the range of conditions experienced in the atmosphere. Microphysical parameterizations employing prognostic moments are known to suffer from structural uncertainty in their representations of inherently higher dimensional cloud processes, which limit model fidelity and lead to forecasting errors. Here we investigate how data‐driven reduced‐order modeling can be used to learn predictors for microphysical process rates in bulk microphysics schemes in an unsupervised manner from higher dimensional bin distributions. Using simulations characteristic of marine stratiform clouds, we simultaneously learn lower dimensional representations of droplet size distributions and predict the evolution of the microphysical state of the system. Droplet collision‐coalescence, the main process for generating warm rain, is estimated to have an intrinsic dimension of three. This intrinsic dimension provides a lower limit on the number of degrees of freedom needed to accurately represent collision‐coalescence in models. We demonstrate how deep learning based reduced‐order modeling can be used to discover intrinsic coordinates describing the microphysical state of the system, where process rates such as collision‐coalescence are globally linearized. These implicitly learned representations of the DSD retain more information about the DSD than typical moment‐based representations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Efficient linear phase contrast in scanning transmission electron microscopy with matched illumination and detector interferometry

The ability to image light elements in soft matter at atomic resolution enables unprecedented insight into the structure and properties of molecular heterostructures and beam-sensitive nanomaterials. In this study, we introduce a scanning transmission electron microscopy technique combining a pre-specimen phase plate designed to produce a probe with structured phase with a high-speed direct electron detector to generate nearly linear contrast images with high efficiency. We demonstrate this method by using both experiment and simulation to simultaneously image the atomic-scale structure of weakly scattering amorphous carbon and strongly scattering gold nanoparticles. Our method demonstrates strong contrast for both materials, making it a promising candidate for structural determination of heterogeneous soft/hard matter samples even at low electron doses comparable to traditional phase-contrast transmission electron microscopy. Ultimately, simulated images demonstrate the extension of this technique to the challenging problem of structural determination of biological material at the surface of inorganic crystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

Acceleration in the linear non-scaling fixed-field alternating-gradient accelerator EMMA

In a fixed-field alternating-gradient (FFAG) accelerator, eliminating pulsed magnet operation permits rapid acceleration to synchrotron energies, but with a much higher beam-pulse repetition rate. Conceived in the 1950s, FFAGs are enjoying renewed interest, fuelled by the need to rapidly accelerate unstable muons for future high-energy physics colliders. Until now a 'scaling' principle has been applied to avoid beam blow-up and loss. Removing this restriction produces a new breed of FFAG, a non-scaling variant, allowing powerful advances in machine characteristics. We report on the first non-scaling FFAG, in which orbits are compacted to within 10?mm in radius over an electron momentum range of 12-18 MeV/c. In this strictly linear-gradient FFAG, unstable beam regions are crossed, but acceleration via a novel serpentine channel is so rapid that no significant beam disruption is observed. This result has significant implications for future particle accelerators, particularly muon and high-intensity proton accelerators.

43 PARTICLE ACCELERATORS↗