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At least 757 records · Page 42

Shedding light on the 239Pu fission source term with new high-precision experiments and advanced fission modeling

In the last decade, there has been a renaissance of fission research resulting in new high-precision experiments and advanced fission modeling. For instance, the Chi-Nu and CEA teams supplied, for the first time, the 239 Pu prompt fission neutron spectrum (PFNS) for broad ranges of incident and outgoing neutron energies. The CEA team also measured 239 Pu average prompt neutron multiplicities, ν ̄ p , with lower statistical uncertainties and a technique significantly different than the one used in the past. The NIFFTE collaboration provided 239 Pu( n ,f)/ 235 U( n ,f) cross section shape ratios with uncertainties below 1% utilizing a novel detector type. Advanced fission event generators were developed, among them CGMF, FIFRELIN, FREYA, and GEF, which calculate post-scission fission observables in a correlated manner. These new experimental data and more consistent fission models change the evaluated PFNS, ν ̄ p , and ( n ,f) cross sections, some only modestly, compared to ENDF/B-VIII.0. In turn, the individual new nuclear data distinctly change simulated effective neutron multiplication factors of fast critical assemblies, but their combined impact is small, while affecting the prediction of LLNL pulsed sphere neutron leakage spectra and reaction rates only within experimental uncertainties. Also, the parameters obtained from fitting to ν ̄ p reproduce various post-scission fission observables within the uncertainties of experimental data. This indicates that new differential experiments and consistent fission modeling reduce compensating errors present in ENDF/B-VIII.0.

fission cross section↗

Boron adatom adsorption on graphene: A case study in computational chemistry methods for surface interactions

Though weak surface interactions and adsorption can play an important role in plasma processing and materials science, they are not necessarily simple to model. A boron adatom adsorbed on a graphene sheet serves as a case study for how carefully one must select the correct technique from a toolbox of computational chemistry methods. Using a variety of molecular dynamics potentials and density functional theory functionals, we evaluate the adsorption energy, investigate barriers to adsorption and migration, calculate corresponding reaction rates, and show that a surprisingly high level of theory may be necessary to verify that the system is described correctly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nuclear data resources and initiatives for nuclear astrophysics

Research into the cosmic synthesis of the elements, the evolution and explosion of stars, the nature of the early Universe, and other important topics in nuclear astrophysics are at the forefront of nuclear science. These studies are motivating laboratory measurements and theoretical calculations that, after significant investments, are pushing the boundaries of what is possible. The latest nuclear results, however, must be specially prepared before they can be used to advance our knowledge of the cosmos. This processing requires a set of resources unique to nuclear astrophysics, and an impressive collection of nuclear reaction and nuclear structure datasets, processing codes, thermonuclear reaction rate libraries, and simulation codes and services have been developed for the field. There are, however, some serious challenges to these efforts that will only worsen in the future, making it important to develop strategies and act now to ensure a sustainable future for this work. After detailing the specific data types needed for nuclear astrophysics and the available data resources, the major challenges in this work and their implications are discussed. A set of initiatives are proposed to meet those challenges along with suggested implementations and possible ways that they may advance our understanding of the Universe and strengthen the field of nuclear astrophysics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

The Reaction of HO2 and CH3O2: CH3OOH Formed from the Singlet Electronic State Surface

High-level coupled-cluster calculations in combination with two-dimensional master equation simulations were used to study the HO2 + CH3O2 reaction, which plays an important role in the oxidation of methane and hydrocarbons in the Earth’s atmosphere and low-temperature combustion. The main reaction pathways taking place on the lowest-lying triplet and singlet potential energy surfaces (PES) were characterized. Interestingly, methyl hydroperoxide (CH3OOH), the sole product, could be produced from both the triplet and singlet PESs, with a ratio of roughly 9:1. Formaldehyde is not made as a primary product, but can be formed via secondary chemistry. The formation of methyl tetraoxide (MTO) from the singlet PES is unimportant. The calculated reaction rate coefficients were found to be practically pressure-independent for p ≤ 760 Torr and can be given by k(T)=2.75×10−13×e+1.75 kcal mol−1/RT (in cm3/s), an expression useful for kinetics modeling over the range T = 200–800 K. The rate constant has a slight negative Arrhenius energy dependence of about −1.75 kcal mol–1, falling about a factor of 30 from 200 K to 800 K.

2DME↗

Data Needs for Modeling Low-Temperature Non-Equilibrium Plasmas: The LXCat Project, History, Perspectives and a Tutorial

Technologies based on non-equilibrium, low-temperature plasmas are ubiquitous in today’s society. Plasma modeling plays an essential role in their understanding, development and optimization. An accurate description of electron and ion collisions with neutrals and their transport is required to correctly describe plasma properties as a function of external parameters. LXCat is an open-access, web-based platform for storing, exchanging and manipulating data needed for modeling the electron and ion components of non-equilibrium, low-temperature plasmas. The data types supported by LXCat are electron- and ion-scattering cross-sections with neutrals (total and differential), interaction potentials, oscillator strengths, and electron- and ion-swarm/transport parameters. Online tools allow users to identify and compare the data through plotting routines, and use the data to generate swarm parameters and reaction rates with the integrated electron Boltzmann solver. In this review, the historical evolution of the project and some perspectives on its future are discussed together with a tutorial review for using data from LXCat.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Electrocatalysts for Using Renewably-Sourced, Organic Electrolytes for Redox Flow Batteries

Biomass could be a source of the redox shuttles that have shown promise for operation as high potential, organic electrolytes for redox flow batteries. There is a sufficient quantity of biomass to satisfy the growing demand to buffer the episodic nature of renewably produced electricity. However, despite a century of effort, it is still not evident how to use existing information from organic electrochemistry to design the electrocatalysts or supporting electrolytes that will confer the required activity, selectivity and longevity. In this research, the use of a fiducial reaction to normalize reaction rates is shown to fail.

09 BIOMASS FUELS↗

Investigations on the Thermal Stability and Kinetics of Biolubricants Synthesized from Different Types of Vegetable Oils

Petroleum-based lubricants raise environmental concerns due to their non-biodegradability and toxicity, whereas biobased lubricants underperform owing to low thermal stability. This study examined and compared three vegetable oils, along with their chemically modified versions, to better understand their suitability as biolubricants. High oleic soybean oil (HOSOY), regular soybean oil (RSOY), and waste cooking oil (WCO) were subjected to chemical modification, where isopropyl groups were attached to the fatty acid chains of the oils to produce branched oils, i.e., b-HOSOY, b-RSOY, and b-WCO. The detailed kinetic study of each regular and modified sample was investigated using thermogravimetric analysis. The kinetic parameters, such as the activation energies, reaction rate, and pre-exponential factor, were generated via Friedman methods. The differential thermal gravimetric (DTG) analysis showed low volatilization at the onset temperature in each modified oil as compared with the unmodified samples under an oxidative environment. Furthermore, the comparative kinetic studies demonstrated the enhanced thermoxidative stability of the modified products relative to their unaltered counterparts. Among the tested oils, the b-RSOY showed an average activation energy of 325 kJ/mol, followed by the b-WCO: 300 kJ/mol and the b-HOSOY: 251 kJ/mol, indicating the most stable modified product under an oxidative environment. For all the samples, the pre-exponential factors were in good agreement with the activation energies, which validates that finding the pre-exponential components is crucial to the kinetic analysis.

Sarker, Majher I. (ORCID:0000000299509274)↗

Extraction Kinetics of Rare Earth Elements from Ion-Adsorbed Underclays

Citric acid has been identified as an environmentally sustainable organic acid capable of leaching up to ~30% of easily accessible REEs from underclay material. An analysis of the leaching profiles was performed to discern the reaction rates, extraction efficiencies, and potential leaching mechanisms of REEs and cations of interest from ion-adsorbed underclays. The initial leaching stage follows a slow intraparticle diffusion mechanism followed by a second stage controlled by a mixed diffusion regime. The leaching profiles of Ca and P were similar to those of REEs, suggesting that REEs are most likely derived from mineral surfaces such as hydroxyapatite or crandallite rather than predominately from underclays. Fitting to a modified diffusion control model found diffusion-controlled leaching to be the primary mechanism whereas non-diffusive mechanisms made up about 22% of the extracted REEs. Gangue cations associated with underclays had less non-diffusive leaching than REE species, indicating that their leaching kinetics may be dominated by diffusion from within the material or potentially from product layer formation. Fitting to Boyd plots further indicated that REEs were leached following intraparticle diffusion control. These results have important implications for the development of more efficient and sustainable methods for extracting REEs or critical minerals from alternative feedstocks.

Prem, Priscilla↗

Dynamics of Laterally Propagating Flames in X-Ray Bursts. II. Realistic Burning and Rotation

In this work, we continue to investigate two-dimensional laterally propagating flames in type I X-ray bursts using fully compressible hydrodynamics simulations. In the current study we relax previous approximations where we artificially boosted the flames. We now use more physically realistic reaction rates, thermal conductivities, and rotation rates, exploring the effects of neutron star rotation rate and thermal structure on the flame. We find that at lower rotation rates the flame becomes harder to ignite, whereas at higher rotation rates the nuclear burning is enhanced by increased confinement from the Coriolis force and the flame propagates steadily. At higher crustal temperatures, the flame moves more quickly and accelerates as it propagates through the atmosphere. If the temperature is too high, instead of a flame propagating across the surface the entire atmosphere burns uniformly. Our findings could have implications for the relationship between observed burst rise times and neutron star rotation and accretion rates. All of the software used for these simulations is freely available.

79 ASTRONOMY AND ASTROPHYSICS↗

Enhanced Nuclear Binding near the Proton Drip Line Opens Possible Bypass of the 64 Ge Rapid Proton Capture Process Waiting Point

Abstract We performed astrophysics model calculations with updated nuclear data to identify a possible bypass of the 64 Ge waiting point, a defining feature of the rapid proton capture (rp) process that powers type I X-ray bursts on accreting neutron stars. We find that the rp-process flow through the 64 Ge bypass could be up to 36% for astrophysically relevant conditions. Our results call for new studies of 65 Se, including the nuclear mass, β -delayed proton emission branching, and nuclear structure as it pertains to the 64 As( p , γ ) reaction rate at X-ray burst temperatures.

Nuclear astrophysics↗

Not-quite-transcendental Functions for Logarithmic Interpolation of Tabulated Data

From tabulated nuclear and degenerate equations of state to photon and neutrino opacities and nuclear reaction rates, tabulated data is ubiquitous in computational astrophysics. The dynamic range that must be covered by these tables typically spans many orders of magnitude. Here we present a novel strategy for accurately and performantly interpolating tabulated data that spans these large dynamic ranges. We demonstrate the efficacy of this strategy in tabulated lookups for nuclear and terrestrial equations of state. We show that this strategy is a faster drop-in replacement for linear interpolation of logarithmic grids.

79 ASTRONOMY AND ASTROPHYSICS↗

The acidity of atmospheric particles and clouds

Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase partitioning of semivolatile gases such as HNO 3 , NH 3 , HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine-particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicate acidity may be relatively constant due to the semivolatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alquimia v1.0: a generic interface to biogeochemical codes – a tool for interoperable development, prototyping and benchmarking for multiphysics simulators

Alquimia v1.0 is a generic interface to geochemical solvers that facilitates development of multiphysics simulators by enabling code coupling, prototyping and benchmarking. The interface enforces the function arguments and their types for setting up, solving, serving up output data and carrying out other common auxiliary tasks while providing a set of structures for data transfer between the multiphysics code driving the simulation and the geochemical solver. Alquimia relies on a single-cell approach that permits operator splitting coupling and parallel computation. We describe the implementation in Alquimia of two widely used open-source codes that perform geochemical calculations: PFLOTRAN and CrunchFlow. We then exemplify its use for the implementation and simulation of reactive transport in porous media by two open-source flow and transport simulators: Amanzi and ParFlow. We also demonstrate its use for the simulation of coupled processes in novel multiphysics applications including the effect of multiphase flow on reaction rates at the pore scale with OpenFOAM, the role of complex biogeochemical processes in land surface models such as the E3SM Land Model (ELM) and the impact of surface–subsurface hydrological interactions on hydrogeochemical export from watersheds with the Advanced Terrestrial Simulator (ATS). These applications make it apparent that the availability of a well-defined yet flexible interface has the potential to improve the software development workflow, freeing up resources to focus on advances in process models and mechanistic understanding of coupled problems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

EPCAPE-PT-LANL Measurements: Proton Transfer Reaction Mass Spectrometer

Coastal cities offer a unique environment for studying aerosol-cloud interactions and the effects of urban emissions on cloud properties. As part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), the Partitioning Thrust by Los Alamos National Laboratory (EPCAPE-PT-LANL) was conducted. Our campaign focused on measuring the optical and chemical properties of aerosols and their interactions within marine stratocumulus clouds in La Jolla, California. EPCAPE-PT-LANL enhances the primary goals of EPCAPE through innovative observations of vapor-phase transitions between aerosols and cloud droplets, the impact of black carbon on aerosol-cloud dynamics, and the effects of cloud processing on aerosol optical properties. Instrument: IONICON High-Resolution PTR-TOF-MS - Trace VOC Analyzer. Concentrations were calculated based on theoretical reaction rates of each species with H3O+. Details of the calculation are found in the PTR-MS Ionicon Manual. Data Notes: It is a high-resolution PTR-TOF-MS we have sub-selected relevant species. Contact us if you want additional data products from this instrument. Header: - CalculatedAcetonitrile[ppbv]: The concentration of acetonitrile expressed in parts per billion by volume (ppbv). - CalculatedAcetaldehyde[ppbv]: The concentration of acetaldehyde expressed in parts per billion by volume (ppbv). - CalculatedAcetone[ppbv]: The concentration of acetone expressed in parts per billion by volume (ppbv). - CalculatedAceticAcid[ppbv]: The concentration of acetic acid expressed in parts per billion by volume (ppbv). - CalculatedIsoprene[ppbv]: The concentration of isoprene expressed in parts per billion by volume (ppbv). - CalculatedMVK[ppbv]: The concentration of methyl vinyl ketone (MVK) and methacrolein (MACR) expressed in parts per billion by volume (ppbv). - CalculatedMEK[ppbv]: The concentration of methyl ethyl ketone (MEK) expressed in parts per billion by volume (ppbv). - CalculatedBenzene[ppbv]: The concentration of benzene expressed in parts per billion by volume (ppbv). - CalculatedToluene[ppbv]: The concentration of toluene expressed in parts per billion by volume (ppbv).

54 ENVIRONMENTAL SCIENCES↗

Microscopic Derivation of Transition-state Theory for Complex Quantum Systems

The decay of quantum complex systems through a potential barrier is often described with transition-state theory, also known as RRKM theory in chemistry. Here we derive the basic formula for transition-state theory based on a generic Hamiltonian as might be constructed in a configuration-interaction basis. Two reservoirs of random Hamiltonians from Gaussian orthogonal ensembles are coupled to intermediate states representing the transition states at a barrier. Under the condition that the decay of the reservoirs to open channels is large, an analytic formula for reaction rates is derived. Here, the transition states act as independent Breit–Wigner resonances which contribute additively to the total transition probability, as is well known for electronic conductance through resonant tunneling states. It is also found that the transition probability is independent of the decay properties of the states in the second reservoir over a wide range of decay widths.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A numerical study on the sooting tendencies of bio-derived fuels for spark-ignition engines

While more efficient vehicles have been developed over the decades, their performance is limited by the properties of existing fuels. In response, the Co-Optimization of Fuels and Engines Initiative (Co-Optima) under the U.S. Department of Energy (DOE) has developed a rigorous screening approach to identify the most promising biomass-derived blendstocks that are suitable for advanced spark-ignition (SI) engines. A detailed kinetic model has also been developed to predict the combustion properties of the selected blendstocks. This kinetic model has been designed mainly targeting ignition and flame propagation properties, and it has not previously been validated for soot formation. In this work, we numerically predicted the sooting tendency of 20 Co-Optima SI blendstocks using the Co-Optima kinetic model. The sooting tendencies are determined quantitatively using the Yield Sooting Index (YSI) methodology. As shown in Fig. 1, the predicted YSIs show good agreement with measurements, except for 2,5-dimethylfuran. We also quantify the sensitivity of the YSI predictions to aromatic growth reactions and fuel decomposition reactions of the test fuels. It is found that PAH growth reactions have little impact on YSIs for all 20 fuels under investigation. On the other hand, fuel decomposition reactions have a significant influence on the YSI of 2,5-dimethylfuran. Perturbing their reaction rates by a factor of two is shown to lead to 11 % YSI prediction uncertainty.

09 BIOMASS FUELS↗

Improvement of SCALE-XSPROC Multigroup Cross Section Processing Based on the CENTRM Pointwise Slowing Down Calculation

The SCALE-XSProc multigroup (MG) cross section processing procedure based on the CENTRM pointwise slowing down calculation is the primary procedure to process problem-dependent self-shielded MG cross sections and scattering matrices for neutron transport calculations.This procedure supports various cell-based geometries including slab, 1-D cylindrical, 1-D spherical and 2-D rectangular configurations and doubly heterogeneous particulate fuels. Recently, this procedure has been significantly improved to be applied to any advanced reactor analysis covering thermal and fast reactor systems, and to be comparable to continuous energy (CE) Monte Carlo calculations. Some reactivity bias and reaction rate differences have been observed compared with CE Monte Carlo calculations, and several areas for improvement have been identified in the SCALE-XSProc MG cross section processing: (1) resonance self-shielding calculations within the unresolved resonance range, (2) 10 eV thermal cut-off energy for the free gas model, (3) on-the-fly adjustments to the thermal scattering matrix, (4) normalization of the pointwise neutron flux, and (5) fine MG energy structure. This procedure ensures very accurate MG cross section processing for high-fidelity deterministic reactor physics analysis for various advanced reactor systems.

Kim, Kang Seog↗

High temperature synthesis for power production and storage

Thermochemical energy storage (TCES) for concentrating solar power (CSP) systems provides higher energy density than sensible energy storage systems. An ammonia-based TCES system dissociates endothermically into hydrogen and nitrogen. The stored energy is released when supercritical hydrogen and nitrogen react exothermically to synthesize ammonia. Prior ammonia synthesis systems are unable to produce temperatures consistent with modern power blocks requiring a working fluid, for example steam or carbon dioxide, to be heated to greater than 600° C., for example about 650° C. An ammonia synthesis system heats steam from, for example 350° C. to 650° C. under pressure of about 26 MPa. The hydrogen and nitrogen are preheated with a flow of supercritical fluid prior to the synthesis step to provide reaction rates sufficient to heat power block working fluid to the desired temperature.

14 SOLAR ENERGY↗