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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Fully thermal meta-GGA exchange correlation free-energy density functional

The application of density functional theory to materials in the warm dense matter regime has motivated the development of exchange-correlation functionals which incorporate proper, explicit temperature dependence. Previous work has yielded fully-thermal exchange-correlation free energy functionals at the local density approximation (LDA) and generalized gradient approximation (GGA) levels of refinement. Recently an additive thermal correction scheme was utilized to construct a meta-GGA exchange-correlation (XC) functional in which thermal effects are treated at the GGA level. Here, the f TSCAN free-energy XC functional presented here includes thermal effects through the meta-GGA level in the context of the SCAN (strongly constrained and appropriately normed) ground-state functional. The f TSCAN functional provides generality while achieving similar performance to a thermal GGA functional at high temperatures, e.g. pressures within 1% of path integral Monte Carlo simulations of warm dense hydrogen, and a significant improvement over ground-state functionals. At low temperatures, f TSCAN demonstrates improvements in accuracy relative to lower-level and deorbitalized functionals, indicating that calculations using f TSCAN may be expected to perform well across experimentally relevant densities and pressures.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Spectral-partitioned Kohn-Sham density functional theory

Here we introduce a general, variational scheme for systematic approximation of a given Kohn-Sham free-energy functional by partitioning the density matrix into distinct spectral domains, each of which may be spanned by an independent diagonal representation without requirement of mutual orthogonality. It is shown that by generalizing the entropic contribution to the free energy to allow for independent representations in each spectral domain, the free energy becomes an upper bound to the exact (unpartitioned) Kohn-Sham free energy, attaining this limit as the representations approach Kohn-Sham eigenfunctions. A numerical procedure is devised for calculation of the generalized entropy associated with spectral partitioning of the density matrix. The result is a powerful framework for Kohn-Sham calculations of systems whose occupied subspaces span multiple energy regimes. As a case in point, we apply the proposed framework to warm- and hot-dense matter described by finite-temperature density functional theory, where at high energies the density matrix is represented by that of the free-electron gas, while at low energies it is variationally optimized. We derive expressions for the spectral-partitioned Kohn-Sham Hamiltonian, atomic forces, and macroscopic stresses within the projector-augmented wave (PAW) and the norm-conserving pseudopotential methods. It is demonstrated that at high temperatures, spectral partitioning facilitates accurate calculations at dramatically reduced computational cost. Moreover, as temperature is increased, fewer exact Kohn-Sham states are required for a given accuracy, leading to further reductions in computational cost. Finally, it is shown that standard multiprojector expansions of electronic orbitals within atomic spheres in the PAW method lack sufficient completeness at high temperatures. Spectral partitioning provides a systematic solution for this fundamental problem.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Chiral algebra, localization, modularity, surface defects, and all that

We study the 2D vertex operator algebra (VOA) construction in 4D N = 2 superconformal field theories on S 3 × S 1 , focusing on both old puzzles and new observations. The VOA lives on a two-torus T 2 ⊂ S 3 × S 1 , it is 1 2 Z -graded, and this torus is equipped with the natural choice of spin structure (1,0) for the Z + 1 2 -graded operators, corresponding to the NS sector vacuum character. By analyzing the possible refinements of the Schur index that preserves the VOA, we find that it admits discrete deformations, which allows access to the remaining spin structures (1,1), (0,1), and (0,0), of which the latter two involve the inclusion of a particular surface defect. For Lagrangian theories, we perform the detailed analysis: we describe the natural supersymmetric background, perform localization, and derive the gauged symplectic boson action on a torus in any spin structure. In the absence of flavor fugacities, the 2D and 4D path integrals precisely match, including the Casimir factors. We further analyze the 2D theory: we identify its integration cycle and the two-point functions and interpret flavor holonomies as screening charges in the VOA. Next, we make some observations about modularity; the T-transformation acts on our four partition functions and lifts to a large diffeomorphism on S 3 × S 1 . More interestingly, we generalize the four partition functions on the torus to an infinite family labeled by both the spin structure and the integration cycle inside the complexified maximal torus of the gauge group. Members of this family transform into one another under the full modular group, and we confirm the recent observation that the S-transform of the Schur index in Lagrangian theories exhibits logarithmic behavior. Finally, we comment on how locally our background reproduces the Ω-background.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Opening band gaps of low-dimensional materials at the meta-GGA level of density functional approximations

The quasiparticle band structure can be properly described by Hedin's GW approximation (GW), at a high computational cost. For band gaps, semilocal density functionals up to the generalized gradient approximation (GGA) level cannot compete with the accuracy of hybrid-based approximations or GW. Meta-GGA density functionals with a strong dependence on the kinetic energy density ingredient can potentially give wider band gaps compared with GGAs. The recent TASK meta-GGA density functional from Aschebrock and Kümmel [ Phys. Rev. Research 1 , 033082 (2019) ], is constructed with an enhanced nonlocality in the generalized Kohn-Sham scheme and therefore harbors great opportunities for band gap prediction. Although this approximation was found to yield excellent band gaps of bulk solids, this accuracy cannot be straightforwardly transferred to low-dimensional materials. Additionally, the reduced screening of these materials results in larger band gaps compared with their bulk counterparts, as an additional barrier to overcome. In this paper we demonstrate how the alteration of this functional affects the band gaps of monolayers and nanoribbons and present accurate band gaps competing with the revised Heyd-Scuseria-Ernzerhof (HSE06) approximation. In order to achieve this goal, we have modified the TASK functional (a) by changing the tight upper bound for one- or two-electron systems ( h X 0 ) from 1.174 to 1.29 and (b) by changing the limit of the interpolation function f X ( α → ∞ ) of the TASK functional that interpolates the exchange enhancement factor F X ( s , α ) from α = 0 to 1. The resulting modified TASK (mTASK) was tested for various materials from three dimensions to two dimensions to one dimension (nanoribbons) and was compared with the results of the higher-level hybrid functional HSE06 or with the G 0 W 0 approximation within many-body perturbation theory. We find that mTASK systematically improves the band gaps and band structures of two-dimensional (2D) and 1D systems, without significantly affecting the accuracy of the original TASK for the bulk 3D materials, when compared with the Perdew-Burke-Ernzerhof (PBE) GGA and the strongly constrained and appropriately normed (SCAN) meta-GGA. We further demonstrate the applicability of mTASK by assessing the band structures of transition metal dichalcogenide nanoribbons with respect to various bending curvatures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A note on higher-order and nonlinear limiting approaches for continuously bounds-preserving discontinuous Galerkin methods

In Dzanic (2024), a limiting approach for high-order discontinuous Galerkin schemes was introduced which allowed for imposing constraints on the solution continuously (i.e., everywhere within the element). While exact for linear constraint functionals, this approach only imposed a sufficient (but not the minimum necessary) amount of limiting for nonlinear constraint functionals. This short note shows how this limiting approach can be extended to allow exactness for general nonlinear quasiconcave constraint functionals through a nonlinear limiting procedure, reducing unnecessary numerical dissipation. Finally, some examples are shown for nonlinear pressure and entropy constraints in the compressible gas dynamics equations, where both analytic and iterative approaches are used.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Generalized kinetic equation for tokamak plasma equilibrium distribution function

A generalised kinetic equation for the equilibrium distribution function in a finite beta, arbitrary tokamak plasma is derived. The equation is correct to second order in ρ/L (ρ is the particle Larmor radius and L is the system size). Resolving finite Larmor radius length scales with no restriction on the ratio of poloidal to total equilibrium magnetic field, B $\vartheta$ /B, it generalises the drift kinetic theory of [Hazeltine Phys. Plasmas 15 (1973) 77] to the limit of B $\vartheta$ /B ~ 1 (e.g. to ensure validity for spherical tokamaks). Two cases are considered. The first provides the equilibrium distribution function, consistent with the generalised gyrokinetic formalism of [Dudkovskaia et al. Plasma Phys. Control. Fusion 65 (2023) 045010], derived specifically to capture neoclassical equilibrium currents in gyrokinetic stability analyses in strong gradient regions. The second assumes short length scales in the direction perpendicular to the magnetic field, which can occur as a result of small coherent magnetic structures in the plasma, such as neoclassical tearing mode magnetic islands close to threshold. This then extends the drift island equations of [Dudkovskaia et al. Nucl. Fusion 63 (2023) 016020] for the plasma response to magnetic islands to a spherical tokamak plasma configuration. In conclusion, resolving ρ ~ ρ $\vartheta$ (or B $\vartheta$ ~ B), where ρ $\vartheta$ is the particle poloidal Larmor radius, is also expected to influence calculations of the magnetic island propagation frequency and the associated contributions to the island onset conditions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Ground State Properties of the Wide Band Gap Semiconductor Beryllium Sulfide (BeS)

We report the results from self-consistent calculations of electronic, transport, and bulk properties of beryllium sulfide (BeS) in the zinc-blende phase, and employed an ab-initio local density approximation (LDA) potential and the linear combination of atomic orbitals (LCAO). We obtained the ground state properties of zb-BeS with the Bagayoko, Zhao, and Williams (BZW) computational method, as enhanced by Ekuma and Franklin (BZW-EF). Our findings include the electronic energy bands, the total (DOS) and partial (pDOS) densities of states, electron and hole effective masses, the equilibrium lattice constant, and the bulk modulus. The calculated band structure clearly shows that zb-BeS has an indirect energy band gap of 5.436 eV, from Γ to a point between Γ and X, for an experimental lattice constant of 4.863 Å. This is in excellent agreement with the experiment, unlike the findings of more than 15 previous density functional theory (DFT) calculations that did not perform the generalized minimization of the energy functional, required by the second DFT theorem, which is inherent to the implementation of our BZW-EF method.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A Framework for Inverse Prediction Using Functional Response Data

Inverse prediction models have commonly been developed to handle scalar data from physical experiments. However, it is not uncommon for data to be collected in functional form. When data are collected in functional form, it must be aggregated to fit the form of traditional methods, which often results in a loss of information. For expensive experiments, this loss of information can be costly. In this study, we introduce the functional inverse prediction (FIP) framework, a general approach which uses the full information in functional response data to provide inverse predictions with probabilistic prediction uncertainties obtained with the bootstrap. The FIP framework is a general methodology that can be modified by practitioners to accommodate many different applications and types of data. We demonstrate the framework, highlighting points of flexibility, with a simulation example and applications to weather data and to nuclear forensics. Results show how functional models can improve the accuracy and precision of predictions.

42 ENGINEERING↗
DOE OSTI2022

Ab-Initio Investigation of Finite Size Effects in Rutile Titania Nanoparticles with Semilocal and Nonlocal Density Functionals

In this work, we employ hybrid and generalized gradient approximation (GGA) level density functional theory (DFT) calculations to investigate the convergence of surface properties and electronic gap of rutile titania nanoparticles with particle size. The surface energies and electronic gaps are calculated for cuboidal particles with minimum dimension ranging from 3.7 Angstrom (24 atoms) to 10.3 Angstrom (384 atoms) using a highly-parallel real-space DFT code to enable hybrid level DFT calculations of larger nanoparticles than are typically practical. We deconvolute the geometric and electronic finite size effects in surface energy, and evaluate the influence of defects on electronic gap and density of states (DOS). The electronic finite size effects in surface energy vanish when the minimum length scale of the nanoparticles becomes greater than 10 Angstrom. We show that this length scale is consistent with a computationally efficient numerical analysis of the characteristic length scale of electronic interactions. The surface energy of nanoparticles having minimum dimension beyond this characteristic length can be approximated using slab calculations that account for the geometric defects. In contrast, the finite size effects on the electronic gap and DOS is highly dependent on the shape and size of these particles. Furthermore, the DOS for cuboidal particles and more realistic particles constructed using the Wulff algorithm reveal that defect states within the electronic gap play a key role in determining the eigen value distribution of nanoparticles and the electronic gap does not converge to the bulk limit for the particle sizes investigated.

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

Self-consistent implementation of locally scaled self-interaction-correction method

Recently proposed local self-interaction correction (LSIC) method is a one-electron self-interaction-correction (SIC) method that uses an iso-orbital indicator to apply the SIC at each point in space by scaling the exchange–correlation and Coulomb energy densities. The LSIC method is exact for the one-electron densities, also recovers the uniform electron gas limit of the uncorrected density functional approximation, and reduces to the well-known Perdew–Zunger SIC (PZSIC) method as a special case. This article presents the self-consistent implementation of the LSIC method using the ratio of Weizsäcker and Kohn–Sham kinetic energy densities as an iso-orbital indicator. The atomic forces as well as the forces on the Fermi-Löwdin orbitals are also implemented for the LSIC energy functional. Results show that LSIC with the simplest local spin density functional predicts atomization energies of the AE6 dataset better than some of the most widely used generalized-gradient-approximation (GGA) functional and barrier heights of the BH6 database better than some of the most widely used hybrid functionals. The LSIC method [a mean absolute error (MAE) of 0.008 Å] predicts bond lengths of a small set of molecules better than the PZSIC-LSDA (MAE 0.042 Å) and LSDA (0.011 Å). Furthermore, this work shows that accurate results can be obtained from the simplest density functional by removing the self-interaction-errors using an appropriately designed SIC method.

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

Diamond surface functionalization via visible light–driven C–H activation for nanoscale quantum sensing

Nitrogen-vacancy (NV) centers in diamond are a promising platform for nanoscale NMR sensing. Despite significant progress toward using NV centers to detect and localize nuclear spins down to the single spin level, NV-based spectroscopy of individual, intact, arbitrary target molecules remains elusive. Such sensing requires that target molecules are immobilized within nanometers of NV centers with long spin coherence. The inert nature of diamond typically requires harsh functionalization techniques such as thermal annealing or plasma processing, limiting the scope of functional groups that can be attached to the surface. Solution-phase chemical methods can be readily generalized to install diverse functional groups, but they have not been widely explored for single-crystal diamond surfaces. Moreover, realizing shallow NV centers with long spin coherence times requires highly ordered single-crystal surfaces, and solution-phase functionalization has not yet been shown with such demanding conditions. In this work, we report a versatile strategy to directly functionalize C–H bonds on single-crystal diamond surfaces under ambient conditions using visible light, forming C–F, C–Cl, C–S, and C–N bonds at the surface. This method is compatible with NV centers within 10 nm of the surface with spin coherence times comparable to the state of the art. As a proof-of-principle demonstration, we use shallow ensembles of NV centers to detect nuclear spins from surface-bound functional groups. Our approach to surface functionalization opens the door to deploying NV centers as a tool for chemical sensing and single-molecule spectroscopy.

Science & Technology - Other Topics↗
DOE OSTI2021

Unraveling the intrinsic atomic physics behind x-ray absorption line shifts in warm dense silicon plasmas

Here, we present a novel free-energy density functional theory (DFT)-based methodology for optical property calculations of warm dense matter to cover a wide range of thermodynamic conditions and photon energies including the entire x-ray range. It uses Mermin–Kohn–Sham density functional theory with exchange-correlation (XC) thermal effects taken into account via a fully temperature dependent generalized gradient approximation XC functional. The methodology incorporates a combination of the ab initio molecular dynamics (AIMD) snapshotted Kubo–Greenwood optic data with a single-atom in simulation cell calculations to close the photon energy gap between the L and K edges and extend the K-edge tail toward many-keV photon energies. This gap arises in the standard scheme due to a prohibitively large number of bands required for the Kubo–Greenwood calculations with AIMD snapshots. Kubo–Greenwood data on snapshots provide an accurate description of optic properties at low photon frequencies slightly beyond the L-edge and x-ray absorption near edges structure (XANES) spectra, while data from periodic calculations with single atoms cover the tail regions beyond the edges. To demonstrate its applicability to mid-Z materials where the standard DFT-based approach is not computationally feasible, we have applied it to opacity calculations of warm dense silicon plasmas. These first-principles calculations revealed a very interesting phenomon of red-to-blue shift in K–L (1s → 2p) and K-edge absorptions along both isotherm and isochore, which are absent in most continuum-lowering models of traditional plasma physics. This new physics phenomenon can be attributed to the underlying competition between the screening of deeply bound core electrons and the screening of outer-shell electrons caused by warm-dense-plasma conditions. We further demonstrate that the ratio of 1s → 2p to the K-edge x-ray absorptions can be used to characterize warm-dense-plasma conditions. Eventually, based on our absorption calculations, we have established a first-principles opacity table (FPOT) for silicon in a wide range of material densities and temperatures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

The Effects of Atmospheric Models on the Estimation of Infrasonic Source Functions at the Source Physics Experiment

We invert infrasound signals for an equivalent seismoacoustic source function using different atmospheric models to produce the necessary Green’s functions. The infrasound signals were produced by a series of underground chemical explosions as part of the Source Physics Experiment (SPE). In a previous study, we inverted the infrasound data using so-called predictive atmospheric models, which were based on historic, regional-scaled, publicly available weather observations interpolated onto a 3D grid. For the work presented here, we invert the same infrasound data, but using atmospheric models based on weather data collected in a time window that includes the approximate time of the explosion experiments, which we term postdictive models. We build two versions of the postdictive models for each SPE event: one that is based solely on the regional scaled observations, and one that is based on both regional scaled observations combined with on-site observations obtained by a weather sonde released at the time of the SPE. We then invert the observed data set three times, once for each atmospheric model type. We find that the estimated seismoacoustic source functions are relatively similar in waveform shape regardless of which atmospheric model that we used to construct the Green’s functions. However, we find that the amplitude of the estimated source functions is systematically dependent on the atmospheric model type: using the predictive atmospheric models to invert the data generally yields estimated source functions that are larger in amplitude than those estimated using the postdictive models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

A Functional Reference Architecture and Assessment Thereof for the National Ignition Facility Industrial Controls Systems

The Industrial Control System (ICS) at the National Ignition Facility (NIF) has an effective, well-established architecture based off a conventional cyclical software paradigm focused on maintainability and the identification of issues. This architecture exhibits scalability in ensuring expansions of the system conform to the existing architecture, modularity enough to allow relatively easy integrations of such expansions and works as a successful tool to introduce control system engineers new to the NIF ICS to the structure of the system at each layer. This architecture, like most software architectures, is object-oriented, lending itself to ease of understanding by control systems engineers and software engineers familiar with an object-oriented perspective. There are occasions, however, where engineers of other disciplines require insight into the functionality and structure of the ICS for the purposes of understanding fundamentally how their own system is or will be governed by the ICS, without the need for the details of operation of the ICS or the object-oriented view. For this reason, a functional architecture of the ICS could be a potent tool for communicating this insight. Even more powerful, a generalization of this proposed functional ICS architecture in the form of a National Ignition Facility and Photon Science (NIF & PS) Industrial Controls Reference Architecture could communicate this insight not just to systems governed by the ICS in the NIF proper, but across entirety of the NIF & PS Principal Associate Directorate (PAD), anywhere an instance of the ICS architecture is present, such as the approximately 40 “small labs” distributed across the directorate. Such a tool will provide an alternative means of understanding the implementation of these control systems, conducive to a larger variety of engineering and scientific disciplines.

42 ENGINEERING↗
DOE OSTI2022

A General Route to Flame Aerosol Synthesis and In Situ Functionalization of Mesoporous Silica

Mesoporous silica is a versatile material for energy, environmental, and medical applications. In this work, for the first time, we report a flame aerosol synthesis method for a class of mesoporous silica with hollow structure and specific surface area exceeding 1000 m 2 /g -1 . We show its superior performance in water purification, drug carrier, and thermal insulation. Moreover, we propose a general route to produce mesoporous nanoshell supported nanocatalysts by in situ decorating active nanoclusters, including noble metal (Pt/SiO 2 ), transition metal (Ni/SiO 2 ), metal oxide (CrO 3 /SiO 2 ), and alumina support (Co/Al 2 O 3 ). As a prototypical application, we perform dry reforming of methane using Ni/SiO 2 , achieving constant 97% CH 4 and CO 2 conversions for more than 200 hours, dramatically outperforming MCM-41 supported Ni catalyst. This work provides a scalable strategy to produce mesoporous nanoshells and proposes an in situ functionalization mechanism to flexible catalysts design for many reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Comparing GGA, GGA+ U , and meta-GGA functionals for redox-dependent binding at open metal sites in metal–organic frameworks

Metal–organic frameworks (MOFs) with open metal sites have been widely investigated for the selective adsorption of small molecules via redox mechanisms where charge transfer can take place between the binding site and the adsorbate of interest. Quantum-chemical screening methods based on density functional theory have emerged as a promising route to accelerate the discovery of MOFs with enhanced binding affinities toward various adsorbates. However, the success of this approach is linked to the accuracy of the underlying density functional approximations (DFAs). In this work, we compare commonly used generalized gradient approximation (GGA), GGA+U, and meta-GGA exchange-correlation functionals in modeling redox-dependent binding at open metal sites in MOFs using O 2 and N 2 as representative small molecules. We find that the self-interaction error inherent to the widely used Perdew, Burke, and Ernzerhof (PBE) GGA predicts metal sites that are artificially redox-active, as evidenced by their strong binding affinities, short metal–adsorbate bond distances, and large degree of charge transfer. The incorporation of metal-specific, empirical Hubbard U corrections based on the transition metal oxide literature systematically reduces the redox activity of the open metal sites, often improving agreement with experiment. Additionally, the binding behavior shifts from strong chemisorption to weaker physisorption as a function of U. The M06-L meta-GGA typically predicts binding energies between those of PBE-D3(BJ) and PBE-D3(BJ)+U when using empirically derived U values from the transition metal oxide literature. Despite the strong sensitivity of the binding affinities toward a given DFA, the GGA, GGA+U, and meta-GGA approaches often yield the same qualitative trends and structure–property relationships.

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

A General Route to Flame Aerosol Synthesis and In Situ Functionalization of Mesoporous Silica

Abstract Mesoporous silica is a versatile material for energy, environmental, and medical applications. Here, for the first time, we report a flame aerosol synthesis method for a class of mesoporous silica with hollow structure and specific surface area exceeding 1000 m 2 g −1 . We show its superior performance in water purification, as a drug carrier, and in thermal insulation. Moreover, we propose a general route to produce mesoporous nanoshell‐supported nanocatalysts by in situ decoration with active nanoclusters, including noble metal (Pt/SiO 2 ), transition metal (Ni/SiO 2 ), metal oxide (CrO 3 /SiO 2 ), and alumina support (Co/Al 2 O 3 ). As a prototypical application, we perform dry reforming of methane using Ni/SiO 2 , achieving constant 97 % CH 4 and CO 2 conversions for more than 200 hours, dramatically outperforming an MCM‐41 supported Ni catalyst. This work provides a scalable strategy to produce mesoporous nanoshells and proposes an in situ functionalization mechanism to design and produce flexible catalysts for many reactions.

Liu, Shuo↗