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At least 1,333 records · Page 74
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Surface Protection and Catalytic CH Alumination

This dataset supports a publication, "Surface Protected Organozirconium Catalyzes C–H Alumination of Saturated Hydrocarbons", and describes the surface-organozirconium catalyzed exchange of ethyl group in AlEt3 for dodecyl or methyl from dodecane or methane. The research describes the benefits of capping remaining surface OH with SiMe3 for improving yields and turnovers. The dataset includes characterization of the precatalyst using solid-state nuclear magnetic resonance spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), as well as gas chromatography and solution NMR of reaction products.

Catalysis and mechanisms of reactions↗
NASA NTRS1987

Numerical simulation of a supersonic reacting mixing layer

In order to arrive at physical models that can adequately describe supersonic combustion, and develop accurate and efficient numerical techniques for the solution of such models' governing equations, a computer program has been developed for the study of reacting flows which considers the multicomponent diffusion and convection of important chemical species, as well as their finite state reaction and the interaction of the fluid mechanics and the chemistry that occurred. The code employs a hybrid Chebyshev pseudospectral technique for integration of the models' resulting governing equations; the program is here used to study a spatially developing and reacting mixing layer.

Drummond, J. Philip↗
NASA NTRS1991

Analysis of opposed-jet hydrogen-air counter flow diffusion flame

An opposed-jet counterflow diffusion-flame configuration is considered for the analysis of a nitrogen-diluted hydrogen-air diffusion flame. A boundary-layer similarity solution is employed in order to reduce the governing equations to a set of equations in one independent variable. The equation set is written in the time-dependent form and solved by the finite-volume time-marching technique. This model uses detailed chemistry and accounts for the variations of Prandtl number and Lewis number as well as the effect of thermal diffusion on the flame. It is noted that a one-step model can predict several features of the flame, while the detailed-chemistry model can be used for fine-tuning the results. The present results indicate that thermal diffusion has negligible effect on the characteristics of the flame.

Ho, Y. H.↗
NASA NTRS2003

Self-Propagating Frontal Polymerization in Water at Ambient Pressure

Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.

Olten, Nesrin↗
NASA NTRSDate not supplied

Variable Lidar Ratios for Marine and Dusty Marine Using MODIS AOD Constrained Retrievals and GOCART Model Simulations and their Impact on Level 2 CALIPSO Data Products in Version 5

The Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) onboard CALIPSO provided global measurements of attenuated backscatter profiles of various tropospheric aerosol species from June 2006 through June 2023. Extinction profiles are retrieved from these backscatter measurements by assuming a value for the extinction-to-backscatter or lidar ratio (LR). Up until version V4.51 of the data products, only a constant global value for each of the species has been used, spatially and temporally. However, it has been well known from various ground-based measurements that LRs of each aerosol species can potentially vary spatially as well seasonally. For the forthcoming Version 5 of the CALIPSO products, the CALIPSO team will implement variable lidar ratios at 532 nm for the species classified as “marine” and “dusty marine”. Here we present the essential elements of this scheme, which involves estimating lidar ratios by constraining Fernald solutions for the CALIOP particulate backscatter profiles using aerosol optical depths (AOD) from collocated MODIS retrievals. To account for the lack of measurements in various regions and seasons (e.g., Arctic winters), we leverage collocated model sea-salt volume fractions (SSVF) simulated by the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and use an empirical relationship between the SSVF and LR to build hybrid climatological maps for the entire globe, i.e., using the modelled values when reliable values of the constrained LRs are not available. Initial evaluation of the resulting extinction profiles and corresponding AODs, both globally and in specific regions are presented using a limited amount of data. The primary improvement in AOD occurs in the coastal areas, like the Arabian Sea and Bay of Bengal. The estimated marine LR values in these regions are significantly higher than the constant value of 23 sr used in previous data releases, likely due to mixing with offshore pollution which results in higher AODs. Initial validation results using the CALIPSO Ocean Derived Column Optical Depth (ODCOD) retrievals and ground-based AERONET AOD measurements are presented.

CALIPSO↗
DOE OSTI2020

IDENTIFICATION OF ADSORBA TION OF ADSORBATE FT-IR BANDS USING IN-SI -IR BANDS USING IN-SITU TECHNIQUES: Pd SPECIATION AND ADSORPTION CHEMISTRY OF Pd-ZEOLITES FOR PASSIVE NOx ADSORPTION

To meet increasingly stringent automotive emissions standards, further improvements in catalytic converter design are necessary. Current automotive catalyst systems are effective at eliminating emission of nitrogen oxides (NOx) once the catalyst reaches operational temperature (~200 °C). NOx emitted at lower catalyst temperatures now comprises most of the NOx released during a typical test cycle. Referred to as “the cold start problem” this issue has come to the forefront of automotive catalyst development, as mitigating these emissions is necessary to further reduce automotive emissions. Passive NOx adsorbers present an appealing solution to the cold start problem, these being a class of materials that chemisorb exhaust components such as NOx, carbon monoxide (CO) and hydrocarbons at near-ambient temperatures, and then desorb these compounds once the downstream catalyst has reached operational temperature. An effective passive NOx adsorber must have several properties: high NOx adsorption at near-ambient temperatures, near-complete NOx desorption at temperatures within the operational range, high thermal stability, and resistance to automotive exhaust components at high temperatures. The potential environmental impact of such a system is substantial, as NOx emissions currently result in the formation of millions of tons of smog and acid rain each year. Pd-exchanged zeolites have shown promise for deployment as Passive NOx adsorbers, though much remains to be understood about their adsorption chemistry and deactivation. In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) provides a convenient probe of adsorbed species, most automotive exhaust components possessing IR-active chemical bonds. By examining the evolution of IR bands under various pretreatments and adsorbates, the overall Pd-speciation and adsorptive zeolite sites of each material can be characterized, and the identities of IR bands can be deduced. In this work, microreactor-MS analysis of the adsorption and desorption behavior of these materials was also examined, these results being coupled with in-situ DRIFTS temperature programmed desorption (TPD) to correlate desorption events with specific adsorbed species. A pair of zeolite frameworks of similar Si/Al ratio but differing pore size were examined, Beta zeolite (BEA) and Chabazite (CHA) representing a medium- and small-pore framework, respectively. The effect of Pd-loading on BEA was examined, as well as the various deactivation pathways and active sites of each material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Copper Reductase Activity and Free Radical Chemistry by Cataract-Associated Human Lens γ-Crystallins

Cataracts are caused by high-molecular weight aggregates of human eye lens proteins that scatter light, causing lens opacity. Metal ions have emerged as important potential players in the etiology of cataract disease, as human lens γ-crystallins are susceptible to metal-induced aggregation. Here, the interaction of Cu 2+ ions with γD-, γC-, and γS- crystallins, the three most abundant γ-crystallins in the lens, has been evaluated. Cu 2+ ions induced non-amyloid aggregation in all three proteins. Solution turbidimetry, SDS-PAGE, circular dichroism and differential scanning calorimetry showed that the mechanism for Cu-induced aggregation involves: i) loss of beta-sheet structure in the N-terminal domain; ii) decreased thermal and kinetic stability; iii) formation of metal-bridged species; and iv) formation of disulfide-bridged dimers. Electron paramagnetic resonance (EPR) revealed two distinct Cu 2+ binding sites in each protein. Spin quantitation demonstrated reduction of γ-crystallin-bound Cu 2+ ions to Cu + under aerobic conditions, while X-ray absorption spectroscopy (XAS) confirmed the presence of linear or trigonal Cu + binding sites in γ-crystallins. Our EPR and XAS studies revealed that γ-crystallins’ Cu 2+ reductase activity yields a protein-based free radical that is likely a Tyr-based species in human γD-crystallin. This unique free radical chemistry carried out by distinct redox-active Cu sites in human lens γ-crystallins likely contributes to the mechanism of copper-induced aggregation. Finally, in the context of an aging human lens, γ-crystallins could be acting, not only as structural proteins, but also as key players for metal and redox homeostasis.

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

Runtime performance of a GAMESS quantum chemistry application offloaded to GPUs

Summary Computational chemistry is at the forefront of solving urgent societal problems, such as polymer upcycling and carbon capture. The complexity of modeling these processes at appropriate length and time scales is mainly manifested in the number and types of chemical species involved in the reactions and may require models of several thousand atoms and large basis sets to accurately capture the chemical complexity and heterogeneity in the physical and chemical processes. The quantum chemistry package General Atomic and Molecular Electronic Structure System (GAMESS) has a wide array of methods that can efficiently and accurately treat complex chemical systems. In this work, we have used the GAMESS Effective Fragment Molecule Orbital (EFMO) method for electronic structure calculation of a challenging mesoporous silica nanoparticle (MSN) model surrounded by about 4700 water molecules to investigate the strong scaling and GPU offloading on hybrid CPU‐GPU nodes. Experiments were performed on the Perlmutter platform at the National Energy Research Scientific Computing Center. Good strong scaling and load balancing have been observed on up to 88 hybrid nodes for different settings of the execution parameters for the calculation considered here. When GPUs are oversubscribed by offloading work from multiple CPU processes, using the NVIDIA multi‐process service (MPS) has consistently reduced time to solution and energy consumed. Additionally, for some configuration parameter settings, oversubscription with MPS improved performance by up to 5.8% over the case without oversubscription.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

ORNL_AISD_NiNb

This dataset describes the nickel-niobium solid solution binary alloy, where the two constituent elements nickel (Ni) and niobium (Nb) are randomly placed on an underlying crystal lattice. This dataset for nickel-niobium (Ni-Nb) alloys available includes the formation energy and bulk modulus for each crystal structure. Each atomic sample has a disordered phase which is obtained starting from an initial regular crystal structure of type body-centered cubic (BCC), face-centered cubic (FCC), or hexagonal compact packed (HCP). The geometry optimization ensures that all the alloy samples reached the equilibrium with negative formation energy. We perform geometry optimizations using the LAMMPS simulation package [1], a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales. We utilized the embedded atom model (EAM) potential for Ni and Nb developed in a previous study [2]. The potential could describe behaviors of the liquid and solid phases of Ni-Nb alloy. The structural factors and angular distributions of three atoms are well-matched with X-ray and ab initio-based molecular dynamics data. We prepared the three different crystals with different initial lattice parameters (3.52 Ã… for FCC, 3.32 Ã… for BCC, and 3.5 Ã… for HCP). We performed energy minimization in two steps. Firstly, we minimized the structures with an isotropic unit cell to minimize the side effects from our arbitrary lattice parameters for all other compositions. Then, we applied geometry optimization with a triclinic (non-orthogonal) unit cell to fully minimize the stress components to calculate the elastic constants. In this procedure, we chose 10,000 as the maximum number of allowable steps aimed at obtaining fully relaxed atomic geometries. The dataset consists of three sets of crystal structures. The first set contains 46,086 irregular crystal structures, each of them with 54 atoms, obtained through optimization starting from a regular BCC crystal structure. The second set contains 24,543 irregular crystal structures, each of them with 32 atoms, obtained through optimization starting from a regular FCC crystal structure. The third set contains 39,303 irregular crystal structures, each of them with 48 atoms, obtained through optimization starting from a regular HCP crystal structure. The atomic configurations within each set span the possible compositional range. The three sets have been unified in a global dataset, which is extremely heterogeneous in terms of crystal structures, lattice volumes, and atomic configurations. Organization of files inside the dataset: the dataset contains three subdirectories called • BCC_opt • FCC_opt • HCP_opt based on the type of initial regular structure used to start the geometry optimization. Inside each of these folders, every atomic structure is identified by a string “A_B_Câ€, where A denotes the number of Nb in the system, B denotes index of structure with a given Nb number, and C denotes the total number of structures generated with a given Nb number. For each optimized crystal structure identified by the unique string of characters “A_B_Câ€, three files are provided: • A_B_C_opt.xyz: The optimized geometries in xyz format • A_B_C_opt.cfg: The optimized geometries in cfg format. It includes cell information and atomic energy, and forces calculated from LAMMPS. • A_B_C.elastic: Raw data of 21 elastic constants from LAMMPS output. • A_B_C.bulk: Calculated upper and lower bounds of bulk modulus and averaged one based on Voigt-Reuss-Hill approach from *.elastic. References: [1] A. P. Thompson, H. M. Aktulga, R. Berger, D. S. Bolintineanu, W. M. Brown, P. S. Crozier, P. J. in 't Veld, A. Kohlmeyer, S. G. Moore, T. D. Nguyen, R. Shan, M. J. Stevens, J. Tranchida, C. Trott, and S. J. Plimpton. LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales. Comp. Phys. Comm., 271:108171, 2022. [2] Y Zhang, R Ashcraft, MI Mendelev, CZ Wang, and KF Kelton. Experimental and molecular dynamics simulation study of structure of liquid and amorphous ni62nb38 alloy. The Journal of chemical physics, 145(20):204505, 2016.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Chemical Functional Groups Regulate Ion Concentrations and pHs in Nanopores

Understanding ion behaviors in functionalized nanopores is essential to deciphering reactions in both natural and engineered systems, such as sediments, biological ion channels, and membranes. While many efforts have shown the modified ion behaviors in the functionalized nanopores, a direct measurement and analysis to show how chemical functional groups affect ion concentrations in nanopores are critically needed. In this work, we present a plasmonic nanosensor that can measure the local concentrations of protons, anions (phosphate, nitrate, sulfate, and arsenate), and cations (mercury, lead, and copper) in functionalized nanopores, and we compare their concentrations in nanopores with the corresponding bulk concentrations. Notably, chemical functional groups induced ion concentrations differently in nanopores. In pristine nanopores and methyl- and phenyl-functionalized nanopores, we discovered an unexpected concurrence of an enhanced anion concentration and a suppressed cation concentration. In addition, the nanopore pH is dependent on bulk solution compositions and can be lower by 2.5 units, even when the bulk solution is well-buffered. In contrast, for hydrophilic (amine, thiol, and carboxyl) nanopores, pH depended on the p K a of the functional groups, and the heavy metal concentrations depended on chemical interactions with the functional groups. Our findings provide a better understanding of water chemistry in nanopores and can help precisely control ions in nanopores to benefit the design of membrane-based desalination techniques, CO 2 storage, and porous catalysts.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Global Pathway Selection with Zero-RK

Global Pathway Selection (GPS) is an algorithm to effectively generates reduced (skeletal) chemistry mechanisms, which speeds up simulations and can be used as a systematic analytics tool to extract insights from complex reacting system. This release is an extension of the original code to run in parallel and to use LLNL's Zero-RK solver for fast solution of chemical problems.

Whitesides, RussellA↗
DOE OSTI2024

TChem-atm v1.0

SAND2024-11300O TChem-atm is a software library that was developed to solve complex kinetic models for atmospheric chemistry applications. TChem-atm interface employs a hierarchical parallelism design to exploit the massive parallelism available from modern computing platforms. It also supports gas atmospheric chemistry applications, e.g., the energy exascale earth system model. TChem can be used as a box model or coupled with a climate model to compute the time evolution of gas tracer species. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Safta, Cosmin↗
DOE OSTI2025

Global Pathway Selection with Zero-RK v0.5

Global Pathway Selection (GPS) is an algorithm to effectively generates reduced (skeletal) chemistry mechanisms, which speeds up simulations and can be used as a systematic analytics tool to extract insights from complex reacting system. This release is an extension of the original code to run in parallel and to use LLNL's Zero-RK solver for fast solution of chemical problems.

Whitesides, RussellA [Lawrence Livermore National ↗
NASA NTRS2012

Masses, Radii, and Cloud Properties of the HR 8799 Planets

The near-infrared colors of the planets directly imaged around the A star HR 8799 are much redder than most field brown dwarfs of the same effective temperature. Previous theoretical studies of these objects have compared the photometric and limited spectral data of the planets to the predictions of various atmosphere and evolution models and concluded that the atmospheres of planets b, c, and d are unusually cloudy or have unusual cloud properties. Most studies have also found that the inferred radii of some or all of the planets disagree with expectations of standard giant planet evolution models. Here we compare the available data to the predictions of our own set of atmospheric and evolution models that have been extensively tested against field L and T dwarfs, including the reddest L dwarfs. Unlike almost all previous studies we specify mutually self-consistent choices for effective temperature, gravity, cloud properties, and planetary radius. This procedure yields plausible and self-consistent values for the masses, effective temperatures, and cloud properties of all three planets. We find that the cloud properties of the HR 8799 planets are in fact not unusual but rather follow previously recognized trends including a gravity dependence on the temperature of the L to T spectral transition, some reasons for which we discuss. We find that the inferred mass of planet b is highly sensitive to the H and K band spectrum. Solutions for planets c and particularly d are less certain but are consistent with the generally accepted constraints on the age of the primary star and orbital dynamics. We also confirm that as for L and T dwarfs and solar system giant planets, non-equilibrium chemistry driven by atmospheric mixing is also important for these objects. Given the preponderance of data suggesting that the L to T spectral type transition is gravity dependent, we present a new evolution calculation that predicts cooling tracks on the near-infrared color-magnitude diagram. Finally we argue that the range of uncertainty conventionally quoted for the bolometric luminosity of all three planets is too small.

Marley, Mark S.↗
NASA NTRS2024

Antarctic polar stratospheric cloud composition as observed by ACE, CALIPSO and MIPAS

The composition of polar stratospheric clouds (PSCs) in the Antarctic is measured by infrared absorption spectroscopy by the Atmospheric Chemistry Experiment (ACE) satellite and compared to lidar (CALIPSO) and emission spectroscopy (MIPAS) results. ACE observations are compared first to CALIPSO for the period 2006–2020, then to MIPAS for the period 2005–2011, and then a set of triple coincidences is studied. In both CALIPSO-ACE and MIPAS-ACE comparisons, nitric acid trihydrate (NAT) detections are in excellent agreement (∼80 % of coincident compositions is found). Supercooled ternary solution (STS) detections are in good agreement for CALIPSO-ACE (∼60 %) but in poor agreement for MIPAS-ACE (39 %). This contrasts with ice detections, in poor agreement for CALIPSO-ACE (∼30 %) and in better agreement for MIPAS-ACE (45 %). Triple coincidences show that ACE STS detections are more reliable than MIPAS STS detections. The comparison between ACE observations and homogeneous CALIPSO PSCs shows that for 11 events, CALIPSO reports STS rather than supercooled nitric acid (SNA) clouds.

Atmospheric Chemistry Experiment↗