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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Numerical case study of the aerosol–cloud interactions in warm boundary layer clouds over the eastern North Atlantic with an interactive chemistry module

The presence of warm boundary layer stratiform clouds over the eastern North Atlantic (ENA) region is commonly influenced by the Azores High, especially during the summer season. To investigate comprehensive aerosol–cloud interactions, this study employs the Weather Research and Forecasting model coupled with a chemistry component (WRF-Chem), incorporating aerosol chemical components that are relevant to the formation of cloud condensation nuclei (CCN) and accounting for aerosol spatiotemporal variation. This study focuses on aerosol indirect effects, particularly the long-range transport of aerosols, in the ENA region under three different weather regimes: a ridge with a surface high-pressure system, a post-trough with a surface high-pressure system, and a weak trough. The WRF-Chem simulations conducted at a near-large-eddy scale offer valuable insights into the model's performance, especially in terms of its ability to use high spatial resolution to capture mesoscale cloud features across various weather regimes. Our result shows that introducing 5 times more aerosols to either non-precipitating or precipitating clouds significantly increases ambient CCN numbers, resulting in, to varying degrees, higher liquid water path (LWP) values. The substantial aerosol–cloud interaction especially occurs in the precipitating clouds and demonstrates the susceptibility of the LWP to changes in CCN under different regimes. Conversely, thin, non-rain clouds at the edges of a cloud system are prone to evaporation, exhibiting an aerosol drying effect. The aerosols released during this process transition back to the accumulation mode, facilitating future activation. This dynamic behavior is not adequately represented in prescribed-aerosol simulations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

Tuning the Surface Structure and Optical Properties of CdSe Clusters Using Coordination Chemistry

A series of nonstoichiometric CdSe clusters with lowest energy electronic absorptions between 409 and 420 nm has been prepared from cadmium 1-naphthoate, 2-naphthoate, 4-thiomethyl-1-naphthaote, and 1-naphthalene thiolate complexes and diphenylphosphine selenide (DPPSe). Pair distribution function analysis of X-ray diffraction data, ligand exchange experiments, and NMR molecular weight analyses suggest the nanocrystal core changes minimally among these clusters despite significant changes to their absorption and luminescence spectra. Photoluminescence excitation spectra obtained at 77 K reveal an energy transfer process between the surface-trapped excited state and the naphthalene-containing ligands that leads to ligand phosphorescence. A Dexter energy transfer mechanism is proposed to explain the observation of ligand phosphorescence on excitation of the cluster. These compounds demonstrate that cluster absorption and trap luminescence can be controlled with surface coordination chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Quantum Chemistry Common Driver and Databases (QCDB) and Quantum Chemistry Engine (QCEngine): Automation and interoperability among computational chemistry programs

We report that community efforts in the computational molecular sciences (CMS) are evolving toward modular, open, and interoperable interfaces that work with existing community codes to provide more functionality and composability than could be achieved with a single program. The Quantum Chemistry Common Driver and Databases (QCDB) project provides such capability through an application programming interface (API) that facilitates interoperability across multiple quantum chemistry software packages. In tandem with the Molecular Sciences Software Institute and their Quantum Chemistry Archive ecosystem, the unique functionalities of several CMS programs are integrated, including CFOUR, GAMESS, NWChem, OpenMM, Psi4, Qcore, TeraChem, and Turbomole, to provide common computational functions, i.e., energy, gradient, and Hessian computations as well as molecular properties such as atomic charges and vibrational frequency analysis. Both standard users and power users benefit from adopting these APIs as they lower the language barrier of input styles and enable a standard layout of variables and data. These designs allow end-to-end interoperable programming of complex computations and provide best practices options by default.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Mesoscale Effects in Electrochemical Conversion: Coupling of Chemistry to Atomic- and Nanoscale Structure in Iron-Based Electrodes

The complex coupling of atomic, chemical, and electronic transformations across multiple length scales underlies the performance of electrochemical energy storage devices. Here, the coupling of chemistry with atomic- and nanoscale structure in iron conversion electrodes is resolved by combining pair distribution function (PDF) and small-angle X-ray scattering (SAXS) analysis for a series of Fe fluorides, oxyfluorides, and oxides. The data show that the anion chemistry of the initial electrode influences the abundance of atomic defects in the Fe atomic lattice. This, in turn, is linked to different atom mobilities and propensity for particle growth. Competitive nanoparticle growth in mixed anion systems contributes to a distinct nanostructure, without the interconnected metallic nanoparticles formed for single anion systems.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Extending molecular simulation time scales: Parallel in time integrations for high-level quantum chemistry and complex force representations

Parallel in time simulation algorithms are presented and applied to conventional molecular dynamics (MD) and ab initio molecular dynamics (AIMD) models of realistic complexity. Assuming that a forward time integrator, f (e.g., Verlet algorithm), is available to propagate the system from time t{sub i} (trajectory positions and velocities x{sub i} = (r{sub i}, v{sub i})) to time t{sub i+1} (x{sub i+1}) by x{sub i+1} = f{sub i}(x{sub i}), the dynamics problem spanning an interval from t{sub 0}…t{sub M} can be transformed into a root finding problem, F(X) = [x{sub i} − f(x{sub (i−1})]{sub i} {sub =1,M} = 0, for the trajectory variables. The root finding problem is solved using a variety of root finding techniques, including quasi-Newton and preconditioned quasi-Newton schemes that are all unconditionally convergent. The algorithms are parallelized by assigning a processor to each time-step entry in the columns of F(X). The relation of this approach to other recently proposed parallel in time methods is discussed, and the effectiveness of various approaches to solving the root finding problem is tested. We demonstrate that more efficient dynamical models based on simplified interactions or coarsening time-steps provide preconditioners for the root finding problem. However, for MD and AIMD simulations, such preconditioners are not required to obtain reasonable convergence and their cost must be considered in the performance of the algorithm. The parallel in time algorithms developed are tested by applying them to MD and AIMD simulations of size and complexity similar to those encountered in present day applications. These include a 1000 Si atom MD simulation using Stillinger-Weber potentials, and a HCl + 4H{sub 2}O AIMD simulation at the MP2 level. The maximum speedup ((serial execution time)/(parallel execution time) ) obtained by parallelizing the Stillinger-Weber MD simulation was nearly 3.0. For the AIMD MP2 simulations, the algorithms achieved speedups of up to 14.3. The parallel in time algorithms can be implemented in a distributed computing environment using very slow transmission control protocol/Internet protocol networks. Scripts written in Python that make calls to a precompiled quantum chemistry package (NWChem) are demonstrated to provide an actual speedup of 8.2 for a 2.5 ps AIMD simulation of HCl + 4H{sub 2}O at the MP2/6-31G* level. Implemented in this way these algorithms can be used for long time high-level AIMD simulations at a modest cost using machines connected by very slow networks such as WiFi, or in different time zones connected by the Internet. The algorithms can also be used with programs that are already parallel. Using these algorithms, we are able to reduce the cost of a MP2/6-311++G(2d,2p) simulation that had reached its maximum possible speedup in the parallelization of the electronic structure calculation from 32 s/time step to 6.9 s/time step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Multi-model Mean Nitrogen and Sulfur Deposition from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Evaluation of Historical and Projected Future Changes

We present multi-model global datasets of nitrogen and sulfate deposition covering time periods from 1850 to 2100, calculated within the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The computed deposition fluxes are compared to surface wet deposition and ice-core measurements. We use a new dataset of wet deposition for 2000-2002 based on critical assessment of the quality of existing regional network data. We show that for present-day (year 2000 ACCMIP time-slice), the ACCMIP results perform similarly to previously published multi-model assessments. The analysis of changes between 1980 and 2000 indicates significant differences between model and measurements over the United States, but less so over Europe. This difference points towards misrepresentation of 1980 NH3 emissions over North America. Based on ice-core records, the 1850 deposition fluxes agree well with Greenland ice cores but the change between 1850 and 2000 seems to be overestimated in the Northern Hemisphere for both nitrogen and sulfur species. Using the Representative Concentration Pathways to define the projected climate and atmospheric chemistry related emissions and concentrations, we find large regional nitrogen deposition increases in 2100 in Latin America, Africa and parts of Asia under some of the scenarios considered. Increases in South Asia are especially large, and are seen in all scenarios, with 2100 values more than double 2000 in some scenarios and reaching >1300 mgN/m2/yr averaged over regional to continental scale regions in RCP 2.6 and 8.5, ~30-50% larger than the values in any region currently (2000). Despite known issues, the new ACCMIP deposition dataset provides novel, consistent and evaluated global gridded deposition fields for use in a wide range of climate and ecological studies.

ACCMIP↗
DOE OSTI2016

Development and validation of chemistry agnostic flow battery cost performance model and application to nonaqueous electrolyte systems: Chemistry agnostic flow battery cost performance model

A chemistry agnostic cost performance model is described for a nonaqueous flow battery. The model predicts flow battery performance by estimating the active reaction zone thickness at each electrode as a function of current density, state of charge, and flow rate using measured data for electrode kinetics, electrolyte conductivity, and electrode-specific surface area. Validation of the model is conducted using a 4kW stack data at various current densities and flow rates. This model is used to estimate the performance of a nonaqueous flow battery with electrode and electrolyte properties used from the literature. The optimized cost for this system is estimated for various power and energy levels using component costs provided by vendors. The model allows optimization of design parameters such as electrode thickness, area, flow path design, and operating parameters such as power density, flow rate, and operating SOC range for various application duty cycles. A parametric analysis is done to identify components and electrode/electrolyte properties with the highest impact on system cost for various application durations. A pathway to 100$kWh -1 for the storage system is identified.

25 ENERGY STORAGE↗
DOE OSTI2016

Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media

Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X‐ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post‐extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface.

Neal, Harrison A.↗
DOE OSTI2022

Comparison of Arctic and Antarctic Stratospheric Climates in Chemistry Versus No‐Chemistry Climate Models

Using nine chemistry-climate and eight associated no-chemistry models, we investigate the persistence and timing of cold episodes occurring in the Arctic and Antarctic stratosphere during the period 1980–2014. We find systematic differences in behavior between members of these model pairs. In a first group of chemistry models whose dynamical configurations mirror their no-chemistry counterparts, we find an increased persistence of such cold polar vortices, such that these cold episodes often start earlier and last longer, relative to the times of occurrence of the lowest temperatures. Also the date of occurrence of the lowest temperatures, both in the Arctic and the Antarctic, is often delayed by 1–3 weeks in chemistry models, versus their no-chemistry counterparts. This behavior exacerbates a widespread problem occurring in most or all models, a delayed occurrence, in the median, of the most anomalously cold day during such cold winters. In a second group of model pairs there are differences beyond just ozone chemistry. In particular, here the chemistry models feature more levels in the stratosphere, a raised model top, and differences in non-orographic gravity wave drag versus their no-chemistry counterparts. Such additional dynamical differences can completely mask the above influence of ozone chemistry. The results point toward a need to retune chemistry-climate models versus their no-chemistry counterparts.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Trimethylsilylcyclopentadienyl (Cp ′ ) Uranium Chemistry: Synthetic and Structural Studies of Cp ′ 4 U and Cp ′ 3 U X ( X = Cl, I, Me)

Cp′ 4 U (Cp′ = C 5 H 4 SiMe 3 ) was synthesized from: (a) KCp′ and [Cp′ 3 U(THF)][BPh 4 ]; (b) Cp′ 3 U and Cp′ 2 Pb; and (c) [K(2.2.2‐cryptand)][Cp′ 4 U] and AgBPh 4 . The compound was identified by X‐ray crystallography as a rare example of a structurally‐characterized tetrakis(cyclopentadienyl)U IV complex. For comparison, the corresponding Th complex, Cp′ 4 Th, was isolated from the direct combination of ThBr 4 (THF) 4 with excess KCp′. During the preparation of Cp′ 3 UMe, the precursor of the [Cp′ 3 U(THF)][BPh 4 ] reagent used above, it was discovered that the reaction of Cp′ 3 UCl and MeLi gives a mixture of Cp′ 3 UMe and Cp′ 3 UCl that can co‐crystallize better than Cp′ 3 UMe in pure form. The Cp′ 3 UMe/Cp′ 3 UCl mixture forms single crystals suitable for X‐ray crystallography and provides a new way to characterize the oil, Cp′ 3 UMe. Cp′ 3 UCl and Cp′ 3 UI were also crystallographically characterized for comparison with the Cp′ 3 UMe/Cp′ 3 UCl crystals.

Windorff, Cory J.↗