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Results for “functional approximation”

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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Descriptors for Electrolyte-Renormalized Oxidative Stability of Solvents in Lithium-Ion Batteries

Electrolyte stability against oxidation is an important factor limiting the development of high energy density batteries. The highest occupied molecular orbital (HOMO) level of solvent molecules has been traditionally used for understanding trends in their oxidative stability, but this assumes a noninteracting environment. However, solvent HOMO levels are renormalized because of molecules in their solvation shells. In this work, we first demonstrate an inexpensive and accurate method to determine the HOMO level of the solvent followed by simple descriptors for renormalization of the HOMO level due to different electrolyte components. The descriptors are based on Gutmann donor and acceptor numbers of the solvent and other components. The method uses fast generalized gradient approximation-level density functional theory calculations compared to previously used expensive, experimental data-dependent methods. This method can be used to screen for unexplored stable solvents among the large number of known organic compounds to design novel high-voltage stable electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2025

Dynamic Metal–Support Interaction Dictates Cu Nanoparticle Sintering on Al 2 O 3 Surfaces

Nanoparticle sintering remains a critical challenge in heterogeneous catalysis. In this work, we present a unified deep potential (DP) model based on the Perdew–Burke–Ernzerhof approximation of density functional theory for Cu nanoparticles on three Al 2 O 3 surfaces (γ-Al 2 O 3 (100), γ-Al 2 O 3 (110), and α-Al 2 O 3 (0001)). Using DP-accelerated simulations, we reveal that the nanoparticle size-mobility relationship strongly depends on the supporting surface. The diffusion of nanoparticles on the two γ-Al 2 O 3 surfaces is almost independent of the size of the nanoparticle, while the diffusion on α-Al 2 O 3 (0001) decreases rapidly with increasing size. Interestingly, nanoparticles with fewer than 55 atoms diffuse several times faster on α-Al 2 O 3 (0001) than on γ-Al 2 O 3 (100) at 800 K while expected to be more sluggish based on their larger binding energy at 0 K. The diffusion on α-Al 2 O 3 (0001) is facilitated by dynamic metal–support interaction (MSI), where Al atoms move out of the surface plane to optimize contact with the nanoparticle and relax back to the plane as the nanoparticle moves away. In contrast, the MSI on γ-Al 2 O 3 (100) and on γ-Al 2 O 3 (110) is dominated by more stable and directional Cu–O bonds, consistent with the limited diffusion observed on these surfaces. Our extended MD simulations provide insight into the sintering processes, showing that the dispersity of the nanoparticles strongly influences the coalescence driven by nanoparticle diffusion. We observed that the coalescence of Cu 13 nanoparticles on α-Al 2 O 3 (0001) can occur in a short time (10 ns) at 800 K even with an initial internanoparticle distance increased to 3 nm, while the coalescence on the two γ-Al 2 O 3 surfaces are inhibited significantly by increasing the initial internanoparticle distance. These findings demonstrate that the dynamics of the supporting surface is crucial to understanding the sintering mechanism and offer guidance for designing sinter-resistant catalysts by engineering the support morphology.

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

Uncertainty Quantification in CO 2 Sequestration Using Surrogate Models from Polynomial Chaos Expansion

In this paper, surrogate models are iteratively built using polynomial chaos expansion (PCE) and detailed numerical simulations of a carbon sequestration system. Output variables from a numerical simulator are approximated as polynomial functions of uncertain parameters. Once generated, PCE representations can be used in place of the numerical simulator and often decrease simulation times by several orders of magnitude. However, PCE models are expensive to derive unless the number of terms in the expansion is moderate, which requires a relatively small number of uncertain variables and a low degree of expansion. To cope with this limitation, instead of using a classical full expansion at each step of an iterative PCE construction method, we introduce a mixed-integer programming (MIP) formulation to identify the best subset of basis terms in the expansion. This approach makes it possible to keep the number of terms small in the expansion. Monte Carlo (MC) simulation is then performed by substituting the values of the uncertain parameters into the closed-form polynomial functions. Based on the results of MC simulation, the uncertainties of injecting CO{sub 2} underground are quantified for a saline aquifer. Moreover, based on the PCE model, we formulate an optimization problem to determine the optimal CO{sub 2} injection rate so as to maximize the gas saturation (residual trapping) during injection, and thereby minimize the chance of leakage.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

First-principles calculation of intrinsic defect chemistry and self-doping in PbTe

Semiconductor dopability is inherently limited by intrinsic defect chemistry. In many thermoelectric materials, narrow band gaps due to strong spin-orbit interactions make accurate atomic level predictions of intrinsic defect chemistry and self-doping computationally challenging. For this study, we use different levels of theory to model point defects in PbTe, and compare and contrast the results against each other and a large body of experimental data. We find that to accurately reproduce the intrinsic defect chemistry and known self-doping behavior of PbTe, it is essential to (a) go beyond the semi-local GGA approximation to density functional theory, (b) include spin-orbit coupling, and (c) utilize many-body GW theory to describe the positions of individual band edges. The hybrid HSE functional with spin-orbit coupling included, in combination with the band edge shifts from G0W0 is the only approach that accurately captures both the intrinsic conductivity type of PbTe as function of synthesis conditions as well as the measured charge carrier concentrations, without the need for experimental inputs. Our results reaffirm the critical role of the position of individual band edges in defect calculations, and demonstrate that dopability can be accurately predicted in such challenging narrow band gap materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Learning continuous models for continuous physics

Abstract Dynamical systems that evolve continuously over time are ubiquitous throughout science and engineering. Machine learning (ML) provides data-driven approaches to model and predict the dynamics of such systems. A core issue with this approach is that ML models are typically trained on discrete data, using ML methodologies that are not aware of underlying continuity properties. This results in models that often do not capture any underlying continuous dynamics—either of the system of interest, or indeed of any related system. To address this challenge, we develop a convergence test based on numerical analysis theory. Our test verifies whether a model has learned a function that accurately approximates an underlying continuous dynamics. Models that fail this test fail to capture relevant dynamics, rendering them of limited utility for many scientific prediction tasks; while models that pass this test enable both better interpolation and better extrapolation in multiple ways. Our results illustrate how principled numerical analysis methods can be coupled with existing ML training/testing methodologies to validate models for science and engineering applications.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2013

Communication: Energy benchmarking with quantum Monte Carlo for water nano-droplets and bulk liquid water

In this work, we show the feasibility of using quantum Monte Carlo (QMC) to compute benchmark energies for configuration samples of thermal-equilibrium water clusters and the bulk liquid containing up to 64 molecules. Evidence that the accuracy of these benchmarks approaches that of basis-set converged coupled-cluster calculations is noted. We illustrate the usefulness of the benchmarks by using them to analyze the errors of the popular BLYP approximation of density functional theory (DFT). Finally, the results indicate the possibility of using QMC as a routine tool for analyzing DFT errors for non-covalent bonding in many types of condensed-phase molecular system.

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

Classical mapping for Hubbard operators: Application to the double-Anderson model

A classical Cartesian mapping for Hubbard operators is developed to describe the nonequilibrium transport of an open quantum system with many electrons. The mapping of the Hubbard operators representing the many-body Hamiltonian is derived by using analogies from classical mappings of boson creation and annihilation operators vis-à-vis a coherent state representation. The approach provides qualitative results for a double quantum dot array (double Anderson impurity model) coupled to fermionic leads for a range of bias voltages, Coulomb couplings, and hopping terms. While the width and height of the conduction peaks show deviations from the master equation approach considered to be accurate in the limit of weak system-leads couplings and high temperatures, the Hubbard mapping captures all transport channels involving transition between many electron states, some of which are not captured by approximate nonequilibrium Green function closures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

The structural diversity of ABS{sub 3} compounds with d{sup 0} electronic configuration for the B-cation

We use first-principles density functional theory within the local density approximation to ascertain the ground state structure of real and theoretical compounds with the formula ABS{sub 3} (A = K, Rb, Cs, Ca, Sr, Ba, Tl, Sn, Pb, and Bi; and B = Sc, Y, Ti, Zr, V, and Nb) under the constraint that B must have a d{sup 0} electronic configuration. Our findings indicate that none of these AB combinations prefer a perovskite ground state with corner-sharing BS{sub 6} octahedra, but that they prefer phases with either edge- or face-sharing motifs. Further, a simple two-dimensional structure field map created from A and B ionic radii provides a neat demarcation between combinations preferring face-sharing versus edge-sharing phases for most of these combinations. We then show that by modifying the common Goldschmidt tolerance factor with a multiplicative term based on the electronegativity difference between A and S, the demarcation between predicted edge-sharing and face-sharing ground state phases is enhanced. We also demonstrate that, by calculating the free energy contribution of phonons, some of these compounds may assume multiple phases as synthesis temperatures are altered, or as ambient temperatures rise or fall.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

All-electron GW quasiparticle band structures of group 14 nitride compounds

We have investigated the group 14 nitrides (M{sub 3}N{sub 4}) in the spinel phase (γ-M{sub 3}N{sub 4} with M = C, Si, Ge, and Sn) and β phase (β-M{sub 3}N{sub 4} with M = Si, Ge, and Sn) using density functional theory with the local density approximation and the GW approximation. The Kohn-Sham energies of these systems have been first calculated within the framework of full-potential linearized augmented plane waves (LAPW) and then corrected using single-shot G{sub 0}W{sub 0} calculations, which we have implemented in the modified version of the Elk full-potential LAPW code. Direct band gaps at the Γ point have been found for spinel-type nitrides γ-M{sub 3}N{sub 4} with M = Si, Ge, and Sn. The corresponding GW-corrected band gaps agree with experiment. We have also found that the GW calculations with and without the plasmon-pole approximation give very similar results, even when the system contains semi-core d electrons. These spinel-type nitrides are novel materials for potential optoelectronic applications because of their direct and tunable band gaps.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Structural and electronic properties of GaAs and GaP semiconductors

The Structural and Electronic properties of Zinc Blende phase of GaAs and GaP compounds are studied using self consistent SIESTA-code, pseudopotentials and Density Functional Theory (DFT) in Local Density Approximation (LDA). The Lattice Constant, Equillibrium Volume, Cohesive Energy per pair, Compressibility and Band Gap are calculated. The band gaps calcultated with DFT using LDA is smaller than the experimental values. The P-V data fitted to third order Birch Murnaghan equation of state provide the Bulk Modulus and its pressure derivatives. Our Structural and Electronic properties estimations are in agreement with available experimental and theoretical data.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Ultra-sensitive pressure dependence of bandgap of rutile-GeO{sub 2} revealed by many body perturbation theory

The reported values of bandgap of rutile GeO{sub 2} calculated by the standard density functional theory within local-density approximation (LDA)/generalized gradient approximation (GGA) show a wide variation (∼2 eV), whose origin remains unresolved. Here, we investigate the reasons for this variation by studying the electronic structure of rutile-GeO{sub 2} using many-body perturbation theory within the GW framework. The bandgap as well as valence bandwidth at Γ-point of rutile phase shows a strong dependence on volume change, which is independent of bandgap underestimation problem of LDA/GGA. This strong dependence originates from a change in hybridization among O-p and Ge-(s and p) orbitals. Furthermore, the parabolic nature of first conduction band along X-Γ-M direction changes towards a linear dispersion with volume expansion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Compositional bowing of band energies and their deformation potentials in strained InGaAs ternary alloys: A first-principles study

Using first-principles calculations, we show that the conduction and valence band energies and their deformation potentials exhibit a non-negligible compositional bowing in strained ternary semiconductor alloys such as InGaAs. The electronic structure of these compounds has been calculated within the framework of local density approximation and hybrid functional approach for large cubic supercells and special quasi-random structures, which represent two kinds of model structures for random alloys. We find that the predicted bowing effect for the band energy deformation potentials is rather insensitive to the choice of the functional and alloy structural model. The direction of bowing is determined by In cations that give a stronger contribution to the formation of the In{sub x}Ga{sub 1−x}As valence band states with x ≳ 0.5, compared to Ga cations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Observations of non-linear plasmon damping in dense plasmas

Here, we present simulations using finite-temperature density-functional-theory molecular-dynamics to calculate dynamic dielectric properties in warm dense aluminum. The comparison between exchange-correlation functionals in the Perdew, Burke, Ernzerhof approximation, Strongly Constrained and Appropriately Normed Semilocal Density Functional, and Heyd, Scuseria, Ernzerhof (HSE) approximation indicates evident differences in the electron transition energies, dc conductivity, and Lorenz number. The HSE calculations show excellent agreement with x-ray scattering data as well as dc conductivity and absorption measurements. These findings demonstrate non-Drude behavior of the dynamic conductivity above the Cooper minimum that needs to be taken into account to determine optical properties in the warm dense matter regime.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Collisional transport coefficients of dense high-temperature plasmas within the quantum Landau-Fokker-Planck framework

In this paper, we extend the long-established formulas for the transport coefficients of classical plasmas inside the dense plasma regime for temperatures and densities where the classical Landau equation breaks down but its quantum extension that includes quantum degeneracy effects is valid. To this end, the quantum Landau kinetic equation is solved by the Chapman-Enskog method. The mathematical derivation is done in full generality, i.e., for multicomponent systems and to all orders of the polynomials expansion used to approximate the distribution functions. We apply the general results to two important examples, the electron gas model and an electron-ion plasma model consisting of one type of ions of any charge. We discuss the combined effects of the Pauli exclusion principle, of the electron-electron, and of the electron-ion collisions on the transport coefficients and on the convergence of the Chapman-Enskog method. For the electron gas model, the effect of the Pauli exclusion principle on the transport coefficients rapidly becomes non-negligible outside the domain of validity of the classical Landau equation. For the electron-ion plasmas, the effect of the Pauli exclusion principle depends sensitively on the ion charge Z and varies non-monotonically with Θ. For instance, for ion charge Z = 1, the electrical conductivity is increased by up to ~30% compared to its classical value over the range of degeneracy parameters studied, the thermal conductivity is reduced by up to ~9%, and the shear viscosity coefficient is increased by up to ~13%. Finally, in the Lorentz gas ( Z → ∞ ) limit, the electrical conductivity is reduced by up to ~14% compared to its classical value over the range of degeneracy parameters studied, the thermal conductivity is reduced by up to ~39%, and the shear viscosity coefficient is not affected.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Learning the temporal evolution of multivariate densities via normalizing flows

In this work, we propose a method to learn multivariate probability distributions using sample path data from stochastic differential equations. Specifically, we consider temporally evolving probability distributions (e.g., those produced by integrating local or nonlocal Fokker–Planck equations). Here, we analyze this evolution through machine learning assisted construction of a time-dependent mapping that takes a reference distribution (say, a Gaussian) to each and every instance of our evolving distribution. If the reference distribution is the initial condition of a Fokker–Planck equation, what we learn is the time-T map of the corresponding solution. Specifically, the learned map is a multivariate normalizing flow that deforms the support of the reference density to the support of each and every density snapshot in time. We demonstrate that this approach can approximate probability density function evolutions in time from observed sampled data for systems driven by both Brownian and Lévy noise. We present examples with two- and three-dimensional, uni- and multimodal distributions to validate the method.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2017

Photoluminescence dynamics of direct and indirect excitons in CdTe/ZnTe superlattices with quantum dot layers

Photoluminescence kinetics is measured for spatially direct and indirect excitons in CdTe quantum dots excited by second harmonic radiation pulses of a picosecond Ti : sapphire laser. The width of a ZnTe barrier layer varied in the range of 2 – 12 monolayers (MLs). Since the photoluminescence decay curves are not described by a single exponential dependence, two components are analysed – fast and slow, which can be approximated by exponential functions. It is shown that in the samples with a barrier layer width of 12 and 4 MLs, the decay times for the fast component of a direct exciton and an indirect exciton are 0.4 ns and 3 μs, respectively. The long-term component is observed in both spectra. For a direct exciton, the photoluminescence decay time is 6 ns, and for an indirect exciton it is 22 μs. It is found that the recombination times for direct and indirect excitons in a sample with the barrier layer width of 2 MLs are close: in both cases the decay time for the fast component and slow component is 2 and 80 ns, respectively. Taking into account the tensile strain of the ZnTe layer and origin of the quantum well for light holes in this layer it is assumed that electrons in CdTe quantum dots interact with light holes in a ZnTe layer and generate a quasi-direct exciton because electron wave functions penetrate into the barrier. (exciton photoluminescence)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Addressing first derivative discontinuities in orbital-optimized opposite-spin scaled second-order perturbation theory with regularization

Orbital-optimized opposite-spin scaled second-order perturbation theory (O 2 ) generates a single-reference wave function composed of approximate Brueckner orbitals with fourth-order computational scaling. While O 2 provides significantly improved treatment of radicals by reducing spin contamination, it has been shown to suffer from first derivative discontinuities for bond stretching near the unrestriction point. That qualitative failure is resolved in this work by the implementation of regularized O 2 , which includes a regularization parameter in the denominator of its second-order term. The value of the regularization parameter is semi-empirically chosen to qualitatively describe bond stretching energetics of hydrogen, ethane and ethene, while also considering the effect of the regularization parameter on thermochemical errors for the well-known Gaussian-2 (G2) test set. The generality of the empirical scaling and semi-empirical regularization parameter is studied by application to the 3dMLBE20, DBH24, RSE43 and W4-11 test sets. We demonstrate that accuracy of O 2 is roughly maintained and sometimes even improved by regularization, with root mean squares of regularised O 2 between factors of 1.6 and 0.8 from corresponding root mean squares of O 2 .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2013

LONGITUDINAL AND RADIAL DEPENDENCE OF SOLAR ENERGETIC PARTICLE PEAK INTENSITIES: STEREO, ACE, SOHO, GOES, AND MESSENGER OBSERVATIONS

Simultaneous measurements of solar energetic particle (SEP) events by two or more of the spacecraft located near 1 AU during the rising phase of solar cycle 24 (i.e., STEREO-A, STEREO-B, and near-Earth spacecraft such as ACE, SOHO, and GOES) are used to determine the longitudinal dependence of 71-112 keV electron, 0.7-3 MeV electron, 15-40 MeV proton, and 25-53 MeV proton peak intensities measured in the prompt component of SEP events. Distributions of the peak intensities for the selected 35 events with identifiable solar origin are approximated by the form exp [ - ({phi} - {phi}{sub 0}){sup 2}/2{sigma}{sup 2}], where {phi} is the longitudinal separation between the parent active region and the footpoint of the nominal interplanetary magnetic field (IMF) line connecting each spacecraft with the Sun, {phi}{sub 0} is the distribution centroid, and {sigma} determines the longitudinal gradient. The MESSENGER spacecraft, at helioradii R < 1 AU, allows us to determine a lower limit to the radial dependence of the 71-112 keV electron peak intensities measured along IMF lines. We find five events for which the nominal magnetic footpoint of MESSENGER was less than 20 Degree-Sign apart from the nominal footpoint of a spacecraft near 1 AU. Although the expected theoretical radial dependence for the peak intensity of the events observed along the same field line can be approximated by a functional form R {sup -{alpha}} with {alpha} < 3, we find two events for which {alpha} > 3. These two cases correspond to SEP events occurring in a complex interplanetary medium that favored the enhancement of peak intensities near Mercury but hindered the SEP transport to 1 AU.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗