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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Search for anomalous gauge couplings in semi-leptonic decays of $WW\gamma$ and $WZ\gamma$ in pp collisions at $\sqrt{s} =$ 8 TeV

A study of the Standard Model (SM) three electroweak boson production, $WV\gamma$ where V = W or Z gauge boson, is presented concerning events with a leptonically decaying W boson accompanied by a photon and two or more jets. We are using the full 2012 dataset, of proton-proton collisions at a center-of-mass energy of 8 TeV and an integrated luminosity of 19.3 fb${}^{-1}$, collected by the CMS detector at the Large Hadron Collider (LHC). $WV\gamma$ production final states may be sensitive to anomalous $WW\gamma\gamma$ and $WWZ\gamma$ quartic couplings. In light of the recent discovery of a Higgs-like particle, we investigate, in a model independent way, any deviation of gauge boson couplings with respect to the SM prediction by setting limits on the anomalous quartic gauge couplings (aQGC) for $WW\gamma\gamma$ and $WWZ\gamma$. Upper limits at 95% confidence level are obtained, with and without a form factor.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2019

Diameter Quality Control of Nb 3 Sn Wires for MQXF Cables in the USA

During this project, the 0.850 ± 0.003 mm Nb 3 Sn wires for the low-beta quadrupole magnets 'MQXFA' procured for the U.S. LHC Accelerator R&D Program (LARP) and the U.S. High Luminosity LHC Accelerator Upgrade Project (US HL-LHC AUP, or simply AUP) are received at Lawrence Berkeley National Laboratory (LBNL). There, the wires are respooled and then fabricated into Rutherford cables for winding coils. As part of the quality control program, AUP obtains from the wire manufacturer values of the maximum, average, minimum, and standard deviation of the two orthogonal axes, which are assessed prior to shipment approval. At LBNL, a dual-axis optical micrometer is used to measure the wire diameter of each spool every ~30 cm prior to cabling. This helps decide whether wire pieces with abnormal diameters should be distributed across the cable cross section, in order to improve cable parameter quality and mechanical stability consistency. This paper presents: 1) diameter data of LARP cables and of the first AUP cables made using wires acquired under LARP; 2) our deviation acceptance/rejection justification; and 3) the impact of wire diameter statistics on cable fabrication.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

A DEEP SEARCH FOR EXTENDED RADIO CONTINUUM EMISSION FROM DWARF SPHEROIDAL GALAXIES: IMPLICATIONS FOR PARTICLE DARK MATTER

We present deep radio observations of four nearby dwarf spheroidal (dSph) galaxies, designed to detect extended synchrotron emission resulting from weakly interacting massive particle (WIMP) dark matter annihilations in their halos. Models by Colafrancesco et al. (CPU07) predict the existence of angularly large, smoothly distributed radio halos in such systems, which stem from electron and positron annihilation products spiraling in a turbulent magnetic field. We map a total of 40.5 deg{sup 2} around the Draco, Ursa Major II, Coma Berenices, and Willman 1 dSphs with the Green Bank Telescope (GBT) at 1.4 GHz to detect this annihilation signature, greatly reducing discrete-source confusion using the NVSS catalog. We achieve a sensitivity of {sigma}{sub sub} {approx}< 7 mJy beam{sup -1} in our discrete source-subtracted maps, implying that the NVSS is highly effective at removing background sources from GBT maps. For Draco we obtained approximately concurrent Very Large Array observations to quantify the variability of the discrete source background, and find it to have a negligible effect on our results. We construct radial surface brightness profiles from each of the subtracted maps, and jackknife the data to quantify the significance of the features therein. At the {approx}10' resolution of our observations, foregrounds contribute a standard deviation of 1.8 mJy beam{sup -1} {<=} {sigma}{sub ast} {<=} 5.7 mJy beam{sup -1} to our high-latitude maps, with the emission in Draco and Coma dominated by foregrounds. On the other hand, we find no significant emission in the Ursa Major II and Willman 1 fields, and explore the implications of non-detections in these fields for particle dark matter using the fiducial models of CPU07. For a WIMP mass M{sub {chi}} = 100 GeV annihilating into b b-bar final states and B = 1 {mu}G, upper limits on the annihilation cross-section for Ursa Major II and Willman I are log (({sigma}v){sub {chi}}, cm{sup 3} s{sup -1}) {approx}< -25 for the preferred set of charged particle propagation parameters adopted by CPU07; this is comparable to that inferred at {gamma}-ray energies from the two-year Fermi Large Area Telescope data. We discuss three avenues for improving the constraints on ({sigma}v){sub {chi}} presented here, and conclude that deep radio observations of dSphs are highly complementary to indirect WIMP searches at higher energies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Frustration-guided motion planning reveals conformational transitions in proteins

Proteins exist as conformational ensembles, exchanging between substates to perform their function. Advances in experimental techniques yield unprecedented access to structural snapshots of their conformational landscape. However, computationally modeling how proteins use collective motions to transition between substates is challenging owing to a rugged landscape and large energy barriers. Here in this paper, we present a new, robotics-inspired motion planning procedure called dCCRRT that navigates the rugged landscape between substates by introducing dynamic, interatomic constraints to modulate frustration. The constraints balance non-native contacts and flexibility, and instantaneously redirect the motion towards sterically favorable conformations. On a test set of eight proteins determined in two conformations separated by, on average, 7.5Å root mean square deviation (RMSD), our pathways reduced the Cα atom RMSD to the goal conformation by 78%, outperforming peer methods. Additionally, we then applied dCC-RRT to examine how collective, small-scale motions of four side-chains in the active site of cyclophilin A propagate through the protein. dCC-RRT uncovered a spatially contiguous network of residues linked by steric interactions and collective motion connecting the active site to a recently proposed, non-canonical capsid binding site 25Å away, rationalizing NMR and multi-temperature crystallography experiments. In all, dCC-RRT can reveal detailed, all-atom molecular mechanisms for small and large amplitude motions.Source code and binaries are freely available at https://github.com/ExcitedStates/KGS/.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Unraveling the Mysteries of Turbulence Transport in a Wind Farm

A true physical understanding of the mysteries involved in the recovery process of the wake momentum deficit, downstream of utility-scale wind turbines in the atmosphere, has not been obtained to date. Field data are not acquired at sufficient spatial and temporal resolutions to dissect some of the mysteries of wake turbulence. It is here that the actuator line method has evolved to become the technology standard in the wind energy community. This work presents the actuator line method embedded into an Open source Field Operation and Manipulation (OpenFOAM) large-eddy simulation solver and applies it to two small wind farms, the first one consisting of an array of two National Renewable Energy Laboratory 5 Megawatt (NREL 5-MW) turbines separated by seven rotor diameters in neutral and unstable atmospheric boundary-layer flow and the second one consisting of five NREL 5-MW wind turbines in unstable atmospheric conditions arranged in two staggered arrays of two and three turbines, respectively. Detailed statistics involving power spectral density (PSD) of turbine power along with standard deviations reveal the effects of atmospheric turbulence and its space and time scales. In conclusion, high-resolution surface data extracts provide new insight into the complex recovery process of the wake momentum deficit governed by turbulence transport phenomena.

17 WIND ENERGY↗
DOE OSTI2024

Elucidating Structural Disorder in Ultra‐Thin Bi‐Rich Bismuth Oxyhalide Photocatalysts

Abstract Advancing the field of photocatalysis requires the elucidation of structural properties that underpin the photocatalytic properties of promising materials. The focus of the present study is layered, Bi‐rich bismuth oxyhalides, which are widely studied for photocatalytic applications yet poorly structurally understood, due to high levels of disorder, nano‐sized domains, and the large number of structurally similar compounds. By connecting insights from multiple scattering techniques, utilizing electron‐, X‐ray‐ and neutron probes, the crystal phase of the synthesized materials is allocated as layered Bi 24 O 31 X 10 (X = Cl, Br), albeit with significant deviation from the reported 3D crystalline model. The materials comprise anisotropic platelet‐shaped crystalline domains, exhibiting significant in‐plane ordering in two dimensions but disorder and an ultra‐thin morphology in the layer stacking direction. Increased synthesis pH tailored larger, more ordered crystalline domains, leading to longer excited state lifetimes determined via femtosecond transient absorption spectroscopy (fs‐TAS). Although this likely contributes to improved photocatalytic properties, assessed via the photooxidation of benzylamine, increasing the overall surface area facilitated the most significant improvement in photocatalytic performance. This study, therefore, enabled both phase allocation and a nuanced discussion of the structure‐property relationship for complicated, ultra‐thin photocatalysts.

Chemistry↗
DOE OSTI2021

Subfield crop yields and temporal stability in thousands of US Midwest fields

Understanding subfield crop yields and temporal stability is critical to better manage crops. Several algorithms have proposed to study within-field temporal variability but they were mostly limited to few fields. In this study, a large dataset composed of 5520 yield maps from 768 fields provided by farmers was used to investigate the influence of subfield yield distribution skewness on temporal variability. The data are used to test two intuitive algorithms for mapping stability: one based on standard deviation and the second based on pixel ranking and percentiles. The analysis of yield monitor data indicates that yield distribution is asymmetric, and it tends to be negatively skewed (p < 0.05) for all of the four crops analyzed, meaning that low yielding areas are lower in frequency but cover a larger range of low values. The mean yield difference between the pixels classified as high-and-stable and the pixels classified as low-and-stable was 1.04 Mg ha –1 for maize, 0.39 Mg ha –1 for cotton, 0.34 Mg ha –1 for soybean, and 0.59 Mg ha —1 for wheat. The yield of the unstable zones was similar to the pixels classified as low-and-stable by the standard deviation algorithm, whereas the two-way outlier algorithm did not exhibit this bias. Furthermore, the increase in the number years of yield maps available induced a modest but significant increase in the certainty of stability classifications, and the proportion of unstable pixels increased with the precipitation heterogeneity between the years comprising the yield maps.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

The effect of laser pulse shape variations on the adiabat of NIF capsule implosions

Indirectly driven capsule implosions on the National Ignition Facility (NIF) [Moses et al., Phys. Plasmas 16, 041006 (2009)] are being performed with the goal of compressing a layer of cryogenic deuterium-tritium (DT) fuel to a sufficiently high areal density (ρR) to sustain the self-propagating burn wave that is required for fusion power gain greater than unity. These implosions are driven with a temporally shaped laser pulse that is carefully tailored to keep the DT fuel on a low adiabat (ratio of fuel pressure to the Fermi degenerate pressure). In this report, the impact of variations in the laser pulse shape (both intentionally and unintentionally imposed) on the in-flight implosion adiabat is examined by comparing the measured shot-to-shot variations in ρR from a large ensemble of DT-layered ignition target implosions on NIF spanning a two-year period. A strong sensitivity to variations in the early-time, low-power foot of the laser pulse is observed. It is shown that very small deviations (∼0.1% of the total pulse energy) in the first 2 ns of the laser pulse can decrease the measured ρR by 50%.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The effects of structure anisotropy on lensing observables in an exact general relativistic setting for precision cosmology

The study of relativistic, higher order, and nonlinear effects has become necessary in recent years in the pursuit of precision cosmology. We develop and apply here a framework to study gravitational lensing in exact models in general relativity that are not restricted to homogeneity and isotropy, and where full nonlinearity and relativistic effects are thus naturally included. We apply the framework to a specific, anisotropic galaxy cluster model which is based on a modified NFW halo density profile and described by the Szekeres metric. We examine the effects of increasing levels of anisotropy in the galaxy cluster on lensing observables like the convergence and shear for various lensing geometries, finding a strong nonlinear response in both the convergence and shear for rays passing through anisotropic regions of the cluster. Deviation from the expected values in a spherically symmetric structure are asymmetric with respect to path direction and thus will persist as a statistical effect when averaged over some ensemble of such clusters. The resulting relative difference in various geometries can be as large as approximately 2%, 8%, and 24% in the measure of convergence (1−κ) for levels of anisotropy of 5%, 10%, and 15%, respectively, as a fraction of total cluster mass. For the total magnitude of shear, the relative difference can grow near the center of the structure to be as large as 15%, 32%, and 44% for the same levels of anisotropy, averaged over the two extreme geometries. The convergence is impacted most strongly for rays which pass in directions along the axis of maximum dipole anisotropy in the structure, while the shear is most strongly impacted for rays which pass in directions orthogonal to this axis, as expected. The rich features found in the lensing signal due to anisotropic substructure are nearly entirely lost when one treats the cluster in the traditional FLRW lensing framework. These effects due to anisotropic structures are thus likely to impact lensing measurements and must be fully examined in an era of precision cosmology.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Simultaneous Unbinned Differential Cross-Section Measurement of Twenty-Four Z+jets Kinematic Observables with the ATLAS Detector

Z boson events at the Large Hadron Collider can be selected with high purity and are sensitive to a diverse range of QCD phenomena. As a result, these events are often used to probe the nature of the strong force, improve Monte Carlo event generators, and search for deviations from standard model predictions. All previous measurements of Z boson production characterize the event properties using a small number of observables and present the results as differential cross sections in predetermined bins. In this analysis, a machine learning method called omnifold is used to produce a simultaneous measurement of twenty-four Z +jets observables using 139 fb -1 of proton-proton collisions at √s =13 TeV collected with the ATLAS detector. Unlike any previous fiducial differential cross-section measurement, this result is presented unbinned as a dataset of particle-level events, allowing for flexible reuse in a variety of contexts and for new observables to be constructed from the twenty-four measured observables.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Structure of disordered TiO 2 phases from ab initio based deep neural network simulations

Amorphous TiO 2 (a-TiO 2 ) is widely used in many fields, ranging from photo-electrochemistry to bio-engineering, hence detailed knowledge of its atomic structure is of scientific and technological interest. Here we use an ab initio-based deep neural network potential (DP) to simulate large scale atomic models of crystalline and disordered TiO 2 with molecular dynamics. Our DP reproduces the structural properties of all (11) TiO 2 crystalline phases, predicts the densities and structure factors of molten and amorphous TiO 2 with only a few percent deviation from experiments, and describes the pressure dependence of the amorphous structure in agreement with recent observations. Furthermore, it can be extended to model additional structures and compositions and can be thus of great value in the study of TiO 2 -based (nano-)materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

SU-E-T-179: Clinical Impact of IMRT Failure Modes at Or Near TG-142 Tolerance Criteria Levels

Purpose: Quantitatively assess the clinical impact of 11 critical IMRT dose delivery failure modes. Methods: Eleven step-and-shoot IMRT failure modes (FMs) were introduced into twelve Pinnacle v9.8 treatment plans. One standard and one highly modulated plan on the IROC IMRT phantom and ten previous H&N patient treatment plans were used. FMs included physics components covered by basic QA near tolerance criteria levels (TG-142) such as beam energy, MLC positioning, and MLC modeling. Resultant DVHs were compared to those of failure-free plans and the severity of plan degradation was assessed considering PTV coverage and OAR and normal tissue tolerances and used for FMEA severity scoring. Six of these FMs were physically simulated and phantom irradiations performed. TLD and radiochromic film results are used for comparison to treatment planning studies. Results: Based on treatment planning studies, the largest clinical impact from the phantom cases was induced by 2 mm systematic MLC shift in one bank with the combination of a D95% target under dose near 16% and OAR overdose near 8%. Cord overdoses of 5%–11% occurred with gantry angle, collimator angle, couch angle, MLC leaf end modeling, and MLC transmission and leakage modeling FMs. PTV coverage and/or OAR sparing was compromised in all FMs introduced in phantom plans with the exception of CT number to electron density tables, MU linearity, and MLC tongue-and-groove modeling. Physical measurements did not entirely agree with treatment planning results. For example, symmetry errors resulted in the largest physically measured discrepancies of up to 3% in the PTVs while a maximum of 0.5% deviation was seen in the treatment planning studies. Patient treatment plan study results are under analysis. Conclusion: Even in the simplistic anatomy of the IROC phantom, some basic physics FMs, just outside of TG-142 tolerance criteria, appear to have the potential for large clinical implications.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2013

ISOCHRONS IN PRESOLAR GRAPHITE GRAINS FROM ORGUEIL

Primitive meteorites contain tiny dust grains that condensed in stellar outflows and explosions. These stardust grains can be extracted from their host meteorites and studied in detail in the laboratory. We investigated depth profiles of the Al-Mg, Ca-K, and Ti-Ca isotopic systems obtained during NanoSIMS isotopic analysis of presolar graphite grains from the CI carbonaceous meteorite Orgueil. Large {sup 26}Al/{sup 27}Al, {sup 41}Ca/{sup 40}Ca, and {sup 44}Ti/{sup 48}Ti ratios, inferred from {sup 26}Mg, {sup 41}K, and {sup 44}Ca excesses from the decay of the short-lived radioisotopes {sup 26}Al, {sup 41}Ca, and {sup 44}Ti, indicate a supernova (SN) origin. From the depth distribution of the radiogenic isotopes and the stable isotopes of their parent elements we constructed isochron-type correlation plots. The plots indicate quantitative retention of radiogenic {sup 26}Mg, {sup 41}K, and {sup 44}Ca in most grains. Deviations from straight lines in the Al-Mg and Ca-K plots can be explained by contamination with {sup 27}Al and isotopically normal Ca, respectively. For the Ti-Ca system in some grains, the lack of parent-daughter correlation indicates either redistribution of radiogenic {sup 44}Ca or heterogeneity in the initial {sup 44}Ti/{sup 48}Ti ratio. We also obtained Si isotopic depth profiles in three graphite grains with large {sup 29}Si and {sup 30}Si excesses, for which a SN origin has been proposed. In two grains no Si-rich subgrains are observed; in the third grain with an apparent Si-rich subgrain the anomalous Si isotopic ratios in the subgrain are the same as in the rest of the graphite host. Our studies show that by measuring depth profiles, information on presolar grains can be obtained that cannot be obtained by whole-grain analysis.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Constraints on f ( R ) and normal-branch Dvali-Gabadadze-Porrati modified gravity model parameters with cluster abundances and galaxy clustering

In this report we present forecasted cosmological constraints from combined measurements of galaxy cluster abundances from the Simons Observatory and galaxy clustering from a DESI-like experiment on two well-studied modified gravity models, the chameleon-screened Hu-Sawicki f(R) model and the nDGP braneworld Vainshtein model. A Fisher analysis is conducted using σ 8 constraints derived from thermal Sunyaev-Zel’dovich (tSZ) selected galaxy clusters as well as linear and quasilinear redshift-space 2-point galaxy correlation functions. We find that the cluster abundances drive the constraints on the nDGP model while f(R) constraints are led by galaxy clustering. The two tracers of the cosmological gravitational field are found to be complementary, and their combination significantly improves constraints on the f(R) in particular in comparison to each individual tracer alone. For a model of f(R) with a general relativity (GR) fiducial case (f R0 = 0), we find a 2-σ upper limit of f R0 ≤ 5.68 x10 -7 . For the well-studied log-based fiducial parameter value in f(R), log 10 (f R0 ) = -5, paired with the parameter value n = 1, we find combined 1-σ constraints of σ(log 10 (f R0 )) = 0.12 and σ(n) = 0.36. For the nDGP model with fiducial n nDGP = 1 we find σ( n nDGP ) = 0.087. Our results present the exciting potential to utilize upcoming galaxy and CMB survey data available in the near future to discern and/or constrain cosmic deviations from GR.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Fluidization of Group A Glass Particles: Experiments and Preliminary Validation

This work is aimed at providing reliable high-quality data from fluidization experiments. Geldart Group A glass beads are used as bed material. The fluidizing medium is air at atmospheric pressure which enters the system at 40% relative humidity. The air inlet velocity is varied over a broad range from 2 U mf to 26 U mf , where the minimum fluidization velocity, U mf , is 0.608 cm/s. There is not a significant change in the mean values of differential pressure; however, there are noticeable trends in their standard deviation values. Preliminary validation studies are performed using the open-source software Multiphase Flow with Interphase eXchanges (MFiX) developed by the National Energy Technology Laboratory (NETL). The results from Eulerian-Eulerian (MFiX-TFM, two-fluid model) and Eulerian-Lagrangian (MFiX-PIC, particle-in-cell) formulations are compared. The work presented in this report highlights the applicability of MFiX-PIC for large-scale applications, and reveals that PIC simulation offers a suitable alternative to TFM simulation when effects due to multiple components or polydispersity are significant. PIC modeling provides a readily extendible framework for such systems. However, PIC models do rely on an empirical closure for inter-particle stress. Some solution discrepancies were evident in MFiX-PIC predictions which require further analysis. As such, the study underlines the need for a systematic approach to quantify the sources of numerical uncertainty within the PIC model. However, even with known empiricism, MFiX-PIC has demonstrated considerable potential in analyzing gas-solid systems. The results obtained are encouraging and warrant further investigation to improve the predictive capability of MFiX-PIC.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Global Validation of a Process-Based Model on Vegetation Gross Primary Production Using Eddy Covariance Observations

Gross Primary Production (GPP) is the largest flux in the global carbon cycle. However, large uncertainties in current global estimations persist. In this study, we examined the performance of a process-based model (Integrated BIosphere Simulator, IBIS) at 62 eddy covariance sites around the world. Our results indicated that the IBIS model explained 60% of the observed variation in daily GPP at all validation sites. Comparison with a satellite-based vegetation model (Eddy Covariance-Light Use Efficiency, EC-LUE) revealed that the IBIS simulations yielded comparable GPP results as the EC-LUE model. Global mean GPP estimated by the IBIS model was 107.50±1.37 Pg C year-1 (mean value ± standard deviation) across the vegetated area for the period 2000–2006, consistent with the results of the EC-LUE model (109.39±1.48 Pg C year-1). To evaluate the uncertainty introduced by the parameter Vcmax, which represents the maximum photosynthetic capacity, we inversed Vcmax using Markov Chain-Monte Carlo (MCMC) procedures. Using the inversed Vcmax values, the simulated global GPP increased by 16.5 Pg C year-1, indicating that IBIS model is sensitive to Vcmax, and large uncertainty exists in model parameterization.

Science & Technology - Other Topics↗
DOE OSTI2014

Structure–property relations of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O

Large single crystals of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O with dimensions up to 40×40×30 mm{sup 3} were grown from aqueous solutions. The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies and their shifts upon variation of pressure, respectively, using the plate-resonance technique. Additionally, the coefficients of thermal expansion were determined between 95 K and 305 K by dilatometry. The elastic behaviour at ambient conditions is dominated by the 2-dimensional network of strong hydrogen bonds within the (001) plane leading to a corresponding pseudo-tetragonal anisotropy of the longitudinal elastic stiffness. The variation of elastic properties with pressure, however, as well as the thermal expansion shows strong deviations from the pseudo-tetragonal symmetry. These deviations are probably correlated with tilts of the elongated tri-nuclear betaine–CuCl{sub 2}–water complexes. Neither the thermal expansion nor the specific heat capacity gives any hint on a phase transition in the investigated temperature range. - Graphical abstract: Single crystal of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O. - Highlights: • Large single crystals (40 ×40 ×30 mm{sup 3}) of [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O were grown. • The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies. • Thermal expansion (95 K–305 K) and heat capacity (113 K–323 K) were determined. • The orthorhombic structure shows pseudo-tetragonal elastic anisotropy at ambient conditions. • The crystal structure is stable in the investigated range (1–1600 bar, 95–303 K)

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

On the prediction of pressure effects for the combination kinetics of two alkyl radicals with the geometric mean rule

Here, alkyl combination reactions, along with their reverse alkane unimolecular decomposition reactions, are widely present in pyrolysis and combustion systems. These reactions occur mainly at temperatures at which their rate coefficients depend on pressure, and only a few studies have explored this dependence for large size alkyls. The accurate calculation of these kinetic data is limited by the size of the alkyl fragments involved, since the theoretical methods used are computationally expensive. Therefore, little reliable data is available for the modeling of real fuels alkane decomposition kinetics. In this paper, we propose an alternative approach that allows an accurate estimation of pressure-dependent kinetic rates for the combination of long-chain alkyl radicals, based on tabulated reaction models. The rates of combination of linear alkyls radicals forming ethane to pentane were calculated using the CASPT2-F12/cc-pVDZ-F12 level within VRC-TST theory combined with master-equation simulations. The computed high-pressure limit rate coefficients showed that n-propyl could be a minimum-size representative structure for larger n-alkyl chain, but this approach fails to capture the pressure dependence of the reaction that remains size-dependent for larger alkyls. The Geometric Mean Rule (GMR), a simple rule that links the self and cross-reactions of three alkyl radicals, is used to address this issue. Our theoretical calculations show for the first time that the GMR applies not only at the high-pressure limit, but also for every pressure explored. The GMR is shown to be accurate, with a maximum 22 % deviation in the falloff region for the estimation of rates for small alkyl combinations. Using this method, we propose a tabulated reaction rate rule for the combination of alkyl radicals up to C5+C5. The use of computed rate coefficients with the GMR approximation opens ways to develop pressure-dependent reaction rate rules for large n-alkyl combinations, based on accurate and computationally expensive theoretical calculations on smaller alkyl fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗