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At least 1,315 records · Page 73

Influence of physical and chemical hydrology on bioremediation of a U-contaminated aquifer informed by reactive transport modeling incorporating 238 U/ 235 U ratios

Microbially-catalyzed reductive immobilization of aqueous uranium (U) as a solid phase has been proposed as a U remediation technique. Both laboratory and field experiments have demonstrated that this reduction reaction alters the 238 U/ 235 U ratio, producing a 238 U-enriched U(IV) solid. In contrast, other major U reactive transport processes fractionate these isotopes much less. This suggests the potential to quantify the extent of bioreduction occurring in groundwater containing U using the 238 U/ 235 U ratio, which would substantially improve upon current practices largely relying on U concentration measurements alone. Current reactive transport models for uranium dynamics include only concentration measurements, which are strongly influenced by highly coupled reactive transformation and aqueous transport processes. The complex physical and chemical behavior of U potentially compromises such quantitative analysis of U storage and release. Here we report the first numerical reactive transport model which explicitly incorporates variations in the 238 U/ 235 U ratio of U and demonstrates improved interpretation of the principal chemical reactions and groundwater transport processes affecting the subsurface mobility and distribution of this widespread contaminant. Recent U bioreduction studies performed in a contaminated aquifer in Rifle, Colorado, USA applied Rayleigh distillation models to interpret U stable isotope fractionation observed as a result of acetate amendment. These simplified models were unable to resolve the spatiotemporal pattern of U isotope fractionation recorded in the aqueous solutes. Here, we employ the multi-component, isotope-enabled CrunchTope reactive transport software to interpret these measured U isotope ratios, and demonstrate accurate reproduction of observed trends in both geochemistry and 238 U/ 235 U ratios for two consecutive years of field experiments. Overall, our results indicate that accurately modeling both the U concentration and isotope ratio distributions greatly constrains the parameter space of the model. We find that the transport properties of U in the Rifle aquifer are governed by the presence of low-permeability regions, which the isotopes are uniquely sensitive to. When U reduction is spatially constrained by these low-permeability regions, the shift in the 238 U/ 235 U ratio becomes more muted. Accurate modeling of observed U isotope ratios thus provides a powerful means to better understand bioremediation, and the current study serves to advance the application of this novel method.

238U/235U↗

Richtmyer–Meshkov instability when a shock is reflected for fluids with arbitrary equation of state

First predicted by Richtmyer in 1960 and experimentally confirmed by Meshkov in 1969, the Richtmyer–Meshkov instability (RMI) is crucial in fields such as physics, astrophysics, inertial confinement fusion and high-energy-density physics. These disciplines often deal with strong shocks moving through condensed materials or high-pressure plasmas that exhibit non-ideal equations of state (EoS), thus requiring theoretical models with realistic fluid EoS for accurate RMI simulations. Approximate formulae for asymptotic growth rates, like those proposed by Richtmyer, are helpful but rely on heuristic prescriptions for compressible materials. These prescriptions can sometimes approximate the RMI growth rate well, but their accuracy remains uncertain without exact solutions, as the fully compressible RMI growth rate is influenced by both vorticity deposited during shock refraction and multiple sonic wave refractions. This study advances previous work by presenting an analytic, fully compressible theory of RMI for reflected shocks with arbitrary EoS. It compares theoretical predictions with heuristic prescriptions using ideal gas, van der Waals gas and three-term constitutive equations for simple metals, the latter being analysed with detailed and simplified ideal-gas-like EoS. We additionally offer an alternative explicit approximate formula for the asymptotic growth rate. The comprehensive model also incorporates the effects of constant-amplitude acoustic waves at the interface, associated with the D'yakov–Kontorovich instability in shocks.

Napieralski, Mario (ORCID:0009000692344901)↗

New generation of effective core potentials from correlated calculations: 2nd row elements

Very recently, we have introduced correlation consistent effective core potentials (ccECPs) derived from many-body approaches with the main target being its use in explicitly correlated methods but also in mainstream approaches. The ccECPs are based on reproducing excitation energies for a subset of valence states, i.e., achieving a near-isospectrality between the original and pseudo Hamiltonians. Additionally, binding curves of dimer molecules have been used for refinement and overall improvement of transferability over a range of bond lengths. Here we apply similar ideas to the second row elements and study several aspects of the constructions in order to find the optimal (or nearly-optimal) solutions within the chosen ECP forms with 3s, 3p valence space (Ne-core). New constructions exhibit accurate low-lying atomic excitations and equilibrium molecular bonds (on average within ≈ 0.03 eV and 3 mA), however, the errors for A1 and Si oxide molecules at short bond lengths are notably larger for both ours and existing ECPs. Assuming this limitation, our ccECPs show a systematic balance between the criteria of atomic spectra accuracy and transferability for molecular bonds. Finally, in order to provide another option with much higher uniform accuracy, we also construct He-core ECPs for the whole row with typical discrepancies of ≈ 0.01 eV or smaller.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid 3D nanoscale coherent imaging via physics-aware deep learning

Phase retrieval, the problem of recovering lost phase information from measured intensity alone, is an inverse problem that is widely faced in various imaging modalities ranging from astronomy to nanoscale imaging. The current process of phase recovery is iterative in nature. As a result, the image formation is time consuming and computationally expensive, precluding real-time imaging. Here, we use 3D nanoscale X-ray imaging as a representative example to develop a deep learning model to address this phase retrieval problem. We introduce 3D-CDI-NN, a deep convolutional neural network and differential programing framework trained to predict 3D structure and strain, solely from input 3D X-ray coherent scattering data. Our networks are designed to be “physics-aware” in multiple aspects; in that the physics of the X-ray scattering process is explicitly enforced in the training of the network, and the training data are drawn from atomistic simulations that are representative of the physics of the material. We further refine the neural network prediction through a physics-based optimization procedure to enable maximum accuracy at lowest computational cost. 3D-CDI-NN can invert a 3D coherent diffraction pattern to real-space structure and strain hundreds of times faster than traditional iterative phase retrieval methods. Our integrated machine learning and differential programing solution to the phase retrieval problem is broadly applicable across inverse problems in other application areas.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A comparison of upwind schemes for computation of three-dimensional hypersonic real-gas flows

The method of Suresh and Liou (1992) is extended, and the resulting explicit noniterative upwind finite-volume algorithm is applied to the integration of 3D parabolized Navier-Stokes equations to model 3D hypersonic real-gas flowfields. The solver is second-order accurate in the marching direction and employs flux-limiters to make the algorithm second-order accurate, with total variation diminishing in the cross-flow direction. The algorithm is used to compute hypersonic flow over a yawed cone and over the Ames All-Body Hypersonic Vehicle. The solutions obtained agree well with other computational results and with experimental data.

Gerbsch, R. A.↗

Relativistic Navigation: A Theoretical Foundation

We present a theoretical foundation for relativistic astronomical measurements in curved space-time. In particular, we discuss a new iterative approach for describing the dynamics of an isolated astronomical N-body system in metric theories of gravity. To do this, we generalize the Fock-Chandrasekhar method of the weak-field and slow-motion approximation (WFSMA) and develop a theory of relativistic reference frames (RF's) for a gravitationally bounded many-extended-body problem. In any proper RF constructed in the immediate vicinity of an arbitrary body, the N-body solutions of the gravitational field equations are formally presented as a sum of the Riemann-flat inertial space-time, the gravitational field generated by the body itself, the unperturbed solutions for each body in the system transformed to the coordinates of this proper RF, and the gravitational interaction term. We develop the basic concept of a general WFSMA theory of the celestial RF's applicable to a wide class of metric theories of gravity and an arbitrary model of matter distribution. We apply the proposed method to general relativity. Celestial bodies are described using a perfect fluid model; as such, they possess any number of internal mass and current multipole moments that explicitly characterize their internal structures. The obtained relativistic corrections to the geodetic equations of motion arise because of a coupling of the bodies' multiple moments to the surrounding gravitational field. The resulting relativistic transformations between the different RF's extend the Poincare group to the motion of deformable self-gravitating bodies. Within the present accuracy of astronomical measurements we discuss the properties of the Fermi-normal-like proper RF that is defined in the immediate vicinity of the extended compact bodies. We further generalize the proposed approximation method and include two Eddington parameters (gamma, Beta). This generalized approach was used to derive the relativistic equations of satellite motion in the vicinity of the extended bodies. Anticipating improvements in radio and laser tracking technologies over the next few decades, we apply this method to spacecraft orbit determination. We emphasize the number of feasible relativistic gravity tests that may be performed within the context of the parameterized WFSMA. Based on the planeto-centric equations of motion of a spacecraft around the planet, we suggested a new null test of the Strong Equivalence Principle (SEP). The experiment to measure the corresponding SEP violation effect could be performed with the future Mercury Orbiter mission. We discuss other relativistic effects, including the perihelion advance and the redshift and geodetic precession of the orbiter's orbital plane about Mercury, as well as the possible future implementation of the proposed formalism in software codes developed for solar-system orbit determination. All the important calculations are completely documented, and the references contain an extensive list of cited literature.

Turyshev, Slava G.↗

A radioisotope - enabled reactive transport model for deep vadose zone carbon

In mountainous regions, which constitute the principle source of recharge to major rivers and regional aquifers, infiltration occurs through fractured, partially saturated, weathered bedrock that acts as a boundary layer between saturated aquifers and surface soil. Commonly this deep vadose zone (DVZ) is many meters thick, and yet its role in regulating the generation, retention and mobility of reactive solutes, including nutrients, contaminants and weathering products, is largely unknown. In particular, many of the key reactions that drive the formation of the weathered DVZ and the quality of water moving through it are redox processes, regulated by the availability of organic carbon and oxygen below the soil layer. The role of the DVZ is thus also poorly constrained in the context of carbon stocks and mobility, particularly in lithologies that are naturally high in organic carbon, such as shales. The overarching hypothesis of this study is that upland regions developed in geologic settings with abundant petrogenic carbon store and actively cycle carbon in the weathered DVZ below the soil and above the water table at rates that are significant and currently unconstrained. In order to quantify this cycling, the current study combines novel instrumentation techniques allowing new direct sampling of DVZ systems with advanced numerical reactive transport simulations of carbon transport and transformation. Critically, these simulations will explicitly treat the three isotopes of carbon (the abundant 12C, the stable rare 13C and the radioactive 14C) in a unified framework, thus clearly parsing between the contributions of modern surface derived carbon and lithologic carbon sources in integrated measurements of fluid and gas phase fluxes. This novel model capability will be applied to test the role of DVZ carbon cycling as a regulator of water quality and geological weathering in two complementary field sites both located in organic carbon rich shale lithologies. The first is the Eel River Critical Zone Observatory (ERCZO) in Mendocino County, California, and the second is the Lawrence Berkeley National Laboratory Watershed Function Scientific Focus Area (SFA) in the East River watershed, near Crested Butte, Colorado. At the ERCZO, a novel vadose zone monitoring system has been installed in a 20 m thick, partially saturated, weathered shale hillslope, and preliminary data already indicate substantial CO2 flux generated many meters below the soil surface. At the SFA field site, an instrumented hillslope transect indicates a more complex multi-dimensional fluid and solute transport regime, which will serve as a key test of the calibrated models. Collectively, this project will advance understanding of the cycling of carbon belowground and in relation to transport pathways across the poorly constrained DVZ characteristic of primary water recharge areas. The key product of this work will be enhanced isotope simulation capabilities that are robust and publicly available for application across a broad diversity of systems.

58 GEOSCIENCES↗

Modeling and Optimization Methods for Controlling and Sizing Grid-connected Energy Storage: A Review

Purpose of Review Energy storage is capable of providing a variety of services and solving a multitude of issues in today's rapidly evolving electric power grid. This paper reviews recent research on modeling and optimization methods for optimally controlling and sizing grid-connected battery energy storage systems (BESSs). Open issues and promising research directions are discussed. Recent Findings Recent studies on BESS dispatch, evaluation, and sizing focus on advanced modeling and optimization methods to maximize stacked value streams from multiple services. BESS models have been improved to better represent operational characteristics or capture degradation effects. Different solution methods and optimization techniques have been proposed to improve the benefits and cost-effectiveness of BESSs, using deterministic approaches prevalently but with impressive progress in capturing and addressing uncertainties. Summary Recent progress in BESS scheduling and sizing better supports planning and operational decision-making in different use cases, which is highly important to advance the deployment of BESSs. Additional research is required to properly model the trade-off between short-term benefits and service life with multiple degradation effects explicitly considered in the decision-making process. Advanced methods are to be developed for effectively determining optimal BESS sizes that maximize overall benefits within a varying lifetime considering diversified system, conditions as well as uncertainties at planning and operational stages.

Wu, Di↗

Reaction Mechanism for the Hydrogen Evolution Reaction on the Basal Plane Sulfur Vacancy Site of MoS 2 Using Grand Canonical Potential Kinetics

We develop the grand canonical potential kinetics (GCP-K) formulation based on thermodynamics from quantum mechanics calculations to provide a fundamental basis for understanding heterogeneous electrochemical reactions. Our GCP-K formulation arises naturally from minimizing the free energy using a Legendre transform relating the net charge of the system and the applied voltage. Performing this macroscopic transformation explicitly allows us to make the connection of GCP-K to the traditional Butler-Volmer kinetics. Using this GCP-K based free energy, we show how to predict both the potential and pH dependent chemistry for a specific example, the hydrogen evolution reaction (HER) at a sulfur vacancy on the basal plane of MoS2.We find that the rate-determining steps in both acidic and basic conditions are the Volmer reaction in which the second hydrogen atom is adsorbed from the solution. Using the GCP-K formulation, we show that the stretched bond distances change continuously as a function of the applied potential. This shows that the main reason for the higher activity in basic conditions is that the transition state is closer to the product, which leads to a more favorable Tafel slope of 60 mV/dec. In contrast if the transition state were closer to the reactant, where the transfer coefficient is less than 0.5 we would obtain a Tafel slope of almost 150 mV/dec. Based on this detailed understanding of the reaction mechanism, we conclude that the second hydrogen at the chalcogenide vacant site is the most active toward the hydrogen evolution reaction. Using this as a descriptor, we compare it to the other 2H group VI metal dichalcogenides and predict that vacancies on MoTe 2 will have the best performance toward HER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Micromechanics analysis of space simulated thermal deformations and stresses in continuous fiber reinforced composites

Space simulated thermally induced deformations and stresses in continuous fiber reinforced composites were investigated with a micromechanics analysis. The investigation focused on two primary areas. First, available explicit expressions for predicting the effective coefficients of thermal expansion (CTEs) for a composite were compared with each other, and with a finite element (FE) analysis, developed specifically for this study. Analytical comparisons were made for a wide range of fiber/matrix systems, and predicted values were compared with experimental data. The second area of investigation focused on the determination of thermally induced stress fields in the individual constituents. Stresses predicted from the FE analysis were compared to those predicted from a closed-form solution to the composite cylinder (CC) model, for two carbon fiber/epoxy composites. A global-local formulation, combining laminated plate theory and FE analysis, was used to determine the stresses in multidirectional laminates. Thermally induced damage initiation predictions were also made.

Bowles, David E.↗

Computations of Internal and External Axisymmetric Nozzle Aerodynamics at Transonic Speeds

Computational Fluid Dynamics (CFD) analyses of axisymmetric circular-arc boattail nozzles have been completed in support of NASA's Next Generation Launch Technology Program to investigate the effects of high-speed nozzle geometries on the nozzle internal flow and the surrounding boattail regions. These computations span the very difficult transonic flight regime, with shock-induced separations and strong adverse pressure gradients. External afterbody and internal nozzle pressure distributions computed with the Wind code are compared with experimental data. A range of turbulence models were examined in Wind, including an Explicit Algebraic Stress model (EASM). Computations on two nozzle geometries have been completed at freestream Mach numbers ranging from 0.6 to 0.9, driven by nozzle pressure ratios (NPR) ranging from 2.9 to 5. Results obtained on converging-only geometry indicate reasonable agreement to experimental data, with the EASM and Shear Stress Transport (SST) turbulence models providing the best agreement. Calculations completed on a converging-diverging geometry involving large-scale internal flow separation did not converge to a true steady-state solution when run with variable timestepping (steady-state). Calculations obtained using constant timestepping (time-accurate) indicate less variations in flow properties compared with steady-state solutions. This failure to converge to a steady-state solution was found to be the result of difficulties in using variable time-stepping with large-scale separations present in the flow. Nevertheless, time-averaged boattail surface pressure coefficient and internal nozzle pressures show fairly good agreement with experimental data. The SST turbulence model demonstrates the best over-all agreement with experimental data.

Dalbello, Teryn↗

The Effect of the Density Ratio on the Nonlinear Dynamics of the Unstable Fluid Interface

Here we report multiple harmonic theoretical solutions for a complete system of conservation laws, which describe the large-scale coherent dynamics in RTI and RMI for fluids with a finite density ratio in the general three-dimensional case. The analysis yields new properties of the bubble front dynamics. In either RTI or RMI, the obtained dependencies of the bubble velocity and curvature on the density ratio differ qualitatively and quantitatively from those suggested by the models of Sharp (1984), Oron et al. (2001), and Goncharov (2002). We show explicitly that these models violate the conservation laws. For the first time, our theory reveals an important qualitative distinction between the dynamics of the RT and RM bubbles.

Abarzhi, S. I.↗

Dispersion of ensembles of non-interacting particles

The dynamics of an ensemble of noninteracting particles dispersing from a common origin and moving in a common force field with an initial distribution of momenta is analyzed using an approach where the particles are considered as a continuum described by a phase-space distribution function. General solutions are obtained for both the distribution function and the associated spatial density function. The linear case of small departures from circular orbits in an axisymmetric gravitational field is treated along with the specific case of particle dispersion from an object in a circular orbit in the same type of field. Numerical results are presented for the latter case, and consideration is given to the inverse problem of determining the initial time and velocity distribution from knowledge of the ensemble structure at a later time. Explicit results are provided for the case of an ellipsoidal distribution of initial momenta, and a numerical procedure is indicated for treating more general cases.

Heard, W. B.↗

Statistical mechanics of dilute liquid mixtures of He3 in He4

The Woo-Tan-Massey quantum-mechanical theory of dilute mixtures of He-3 in liquid He-4 is extended to incorporate superfluid flow. Then statistical-mechanical principles are employed to find explicit formulas for thermodyanmic and hydrodynamic properties of mixtures, such as internal energy, free energy, entropy, pressure, chemical potential, and normal-fluid and superfluid densities. This paper is the first in a planned series that applies methods originally developed for pure liquid He-4 to dilute mixtures as a means of establishing a comprehensive theory that includes a theoretical bridge between a microscopic description of the mixtures and a hydrodynamic two-fluid model. Ultimately effects of applied electric and magnetic fields on dilute solutions are also planned to be treated.

Jackson, H. W.↗

Chemical application of diffusion quantum Monte Carlo

The diffusion quantum Monte Carlo (QMC) method gives a stochastic solution to the Schroedinger equation. This approach is receiving increasing attention in chemical applications as a result of its high accuracy. However, reducing statistical uncertainty remains a priority because chemical effects are often obtained as small differences of large numbers. As an example, the single-triplet splitting of the energy of the methylene molecule CH sub 2 is given. The QMC algorithm was implemented on the CYBER 205, first as a direct transcription of the algorithm running on the VAX 11/780, and second by explicitly writing vector code for all loops longer than a crossover length C. The speed of the codes relative to one another as a function of C, and relative to the VAX, are discussed. The computational time dependence obtained versus the number of basis functions is discussed and this is compared with that obtained from traditional quantum chemistry codes and that obtained from traditional computer architectures.

Reynolds, P. J.↗

Mixing and Transition Control Studied

Considerable progress in understanding nonlinear phenomena in both unbounded and wallbounded shear flow transition has been made through the use of a combination of high- Reynolds-number asymptotic and numerical methods. The objective of this continuing work is to fully understand the nonlinear dynamics so that ultimately (1) an effective means of mixing and transition control can be developed and (2) the source terms in the aeroacoustic noise problem can be modeled more accurately. Two important aspects of the work are that (1) the disturbances evolve from strictly linear instability waves on weakly nonparallel mean flows so that the proper upstream conditions are applied in the nonlinear or wave-interaction streamwise region and (2) the asymptotic formulations lead to parabolic problems so that the question of proper out-flow boundary conditions--still a research issue for direct numerical simulations of convectively unstable shear flows--does not arise. Composite expansion techniques are used to obtain solutions that account for both mean-flow-evolution and nonlinear effects. A previously derived theory for the amplitude evolution of a two-dimensional instability wave in an incompressible mixing layer (which is in quantitative agreement with available experimental data for the first nonlinear saturation stage for a plane-jet shear layer, a circular-jet shear layer, and a mixing layer behind a splitter plate) have been extended to include a wave-interaction stage with a three-dimensional subharmonic. The ultimate wave interaction effects can either give rise to explosive growth or an equilibrium solution, both of which are intimately associated with the nonlinear self-interaction of the three dimensional component. The extended theory is being evaluated numerically. In contrast to the mixing-layer situation, earlier comparisons of theoretical predictions based on asymptotic methods and experiments in wall-bounded shear-flow transition have been somewhat lacking in one aspect or another. The current work strongly suggests that the main weakness is the underlying asymptotic representation of the linear "part" of the problem and not the explicit modeling of the nonlinear/wave-interaction effects. Consequently, the long-wave-length/high-Reynolds-number asymptotic limit for the Blasius boundary-layer stability problem was reexamined, and a new dispersion relationship for the instability waves that is uniformly valid for both the upper- and lower branch regions to the required order of approximation was obtained. A comparison with numerical results, obtained by solving the Orr-Sommerfeld stability problem, shows that the asymptotic formula provides surprisingly good results, even for values of the frequency parameter usually encountered in experimental investigations. This is particularly evident in the dynamically important upper-branch region, where much of the nonlinear interactions in transition experiments are believed to take place. The result is important in that it can be used to greatly improve the accuracy of weakly nonlinear critical-layer-based theories, and a consistent nonlinear theory is currently under evaluation.

Source record↗

Downward quantum learning from element 118: Automated generation of Fermi–Löwdin orbitals for all atoms

A new algorithm based on a rigorous theorem and quantum data computationally mined from element 118 guarantees automated construction of initial Fermi–Löwdin-Orbital (FLO) starting points for all elements in the Periodic Table. It defines a means for constructing a small library of scalable FLOs for universal use in molecular and solid-state calculations. The method can be systematically improved for greater efficiency and for applications to excited states such as x-ray excitations and optically silent excitations. FLOs were introduced to recast the Perdew–Zunger self-interaction correction (PZSIC) into an explicit unitarily invariant form. The FLOs are generated from a set of N quasi-classical electron positions, referred to as Fermi-Orbital descriptors (FODs), and a set of N-orthonormal single-electron orbitals. FOD positions, when optimized, minimize the PZSIC total energy. However, creating sets of starting FODs that lead to a positive definite Fermi orbital overlap matrix has proven to be challenging for systems composed of open-shell atoms and ions. The proof herein guarantees the existence of a FLOSIC solution and further guarantees that if a solution for N electrons is found, it can be used to generate a minimum of N – 1 and a maximum of 2 N – 2 initial starting points for systems composed of a smaller number of electrons. As a result, applications to heavy and super-heavy atoms are presented. All starting solutions reported here were obtained from a solution for element 118, Oganesson.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fourier Analyses of High-Order Continuous and Discontinuous Galerkin Methods

In this paper, we present a Fourier analysis of wave propagation problems subject to a class of continuous and discontinuous discretizations using high-degree Lagrange polynomials. This allows us to obtain explicit analytical formulas for the dispersion relation and group velocity and, for the first time to our knowledge, characterize analytically the emergence of gaps in the dispersion relation at specific wavenumbers, when they exist, and compute their specific locations. Wave packets with energy at these wavenumbers will fail to propagate correctly, leading to significant numerical dispersion. We also show that the Fourier analysis generates mathematical artifacts, and we explain how to remove them through a branch selection procedure conducted by analysis of eigenvectors and associated reconstructed solutions. The higher frequency eigenmodes, named erratic in this study, are also investigated analytically and numerically.

97 MATHEMATICS AND COMPUTING↗