Results for “energy density functional” — Page 76

DOE OSTI2024

Real-Space Pseudopotential Method for the Calculation of Third-Row Elements X-ray Photoelectron Spectroscopic Signatures

X-ray photoelectron spectroscopy (XPS) is a powerful characterization technique that unveils subtle chemical environment differences via core– electron binding energy (CEBE) analysis. We extend the development of realspace pseudopotential methods to calculating 1s, 2s, and 2p 3/2 CEBEs of third-row elements (S, P, and Si) within the framework of Kohn–Sham density-functional theory (KS-DFT). The new approach systematically prevents variational collapse and simplifies core-excited orbital selection within dense energy level distributions. However, careful error cancellation analysis is required to achieve accuracy comparable to all-electron methods and experiments. Combined with real-space KS-DFT implementation, this development enables large-scale simulations with both Dirichlet boundary conditions and periodic boundary conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Unraveling H2 chemisorption and physisorption on metal decorated graphene using quantum Monte Carlo

Molecular hydrogen has the potential to significantly reduce the use of carbon dioxide emitting energy processes. However, hydrogen gas storage is a major bottleneck for its large-scale use as current storage methods are energy intensive. Among different storage methods, physisorbing molecular hydrogen at ambient pressure and temperatures is a promising alternative—particularly in light of the advancements in tunable lightweight nanomaterials and high throughput screening methods. Nonetheless, understanding hydrogen adsorption in well-defined nanomaterials remains experimentally challenging and reference information is scarce despite the proliferation of works predicting hydrogen adsorption. We focus on Li, Na, Ca, and K, decorated graphene sheets as substrates for molecular hydrogen adsorption, and compute the most accurate adsorption energies available to date using quantum diffusion Monte Carlo (DMC). Building on our previous insights at the density functional theory (DFT) level, we find that a weak covalent chemisorption of molecular hydrogen, known as Kubas interaction, is feasible on Ca decorated graphene according to DMC, in agreement with DFT. This finding is in contrast to previous DMC predictions of the 4H2/Ca+ gas cluster (without graphene) where chemisorption is not favored. However, we find that the adsorption energy of hydrogen on metal decorated graphene according to a widely used DFT method is not fully consistent with DMC. The reference adsorption energies reported herein can be used to find better work-horse methods for application in large-scale modeling of hydrogen adsorption. Furthermore, the implications of this work affect strategies for finding suitable hydrogen storage materials and high-throughput methods.

Chemistry↗

DOE OSTI2023

Defect graph neural networks for materials discovery in high-temperature clean-energy applications

We present a graph neural network approach that fully automates the prediction of defect formation enthalpies for any crystallographic site from the ideal crystal structure, without the need to create defected atomic structure models as input. Here we used density functional theory reference data for vacancy defects in oxides, to train a defect graph neural network (dGNN) model that replaces the density functional theory supercell relaxations otherwise required for each symmetrically unique crystal site. Interfaced with thermodynamic calculations of reduction entropies and associated free energies, the dGNN model is applied to the screening of oxides in the Materials Project database, connecting the zero-kelvin defect enthalpies to high-temperature process conditions relevant for solar thermochemical hydrogen production and other energy applications. The dGNN approach is applicable to arbitrary structures with an accuracy limited principally by the amount and diversity of the training data, and it is generalizable to other defect types and advanced graph convolution architectures. In conclusion, it will help to tackle future materials discovery problems in clean energy and beyond.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2023

High-throughput ab initio reaction mechanism exploration in the cloud with automated multi-reference validation

Quantum chemical calculations on atomistic systems have evolved into a standard approach to studying molecular matter. These calculations often involve a significant amount of manual input and expertise, although most of this effort could be automated, which would alleviate the need for expertise in software and hardware accessibility. Here, we present the AutoRXN workflow, an automated workflow for exploratory high-throughput electronic structure calculations of molecular systems, in which (i) density functional theory methods are exploited to deliver minimum and transition-state structures and corresponding energies and properties, (ii) coupled cluster calculations are then launched for optimized structures to provide more accurate energy and property estimates, and (iii) multi-reference diagnostics are evaluated to back check the coupled cluster results and subject them to automated multi-configurational calculations for potential multi-configurational cases. All calculations are carried out in a cloud environment and support massive computational campaigns. Key features of all components of the AutoRXN workflow are autonomy, stability, and minimum operator interference. We highlight the AutoRXN workflow with the example of an autonomous reaction mechanism exploration of the mode of action of a homogeneous catalyst for the asymmetric reduction of ketones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Photophysical properties of zero-dimensional perovskites studied by PBE0 and GW+BSE methods

Due to the exceptional photophysical properties and great potential applications in solid state lighting, zero-dimensional halide perovskites with broadband emitting have recently attracted much attention. In this work, to reveal the origin of the broadband absorption and emission spectra of 0D (C 4 N 2 H 14 Br) 4 SnBr x I 6-x (x = 3), the ground state and exciton dynamics properties have been studied by hybrid PBE0 functional and the GW+BSE method. Different self-trapped excitons (STEs) are obtained, and their emission energies by PBE0 are consistent well with experimental data. By considering the vibrational broadening of emission, our calculated full width at half maximum of emission accords well with the experiment. The absorption of free exciton and STEs is also calculated by considering the quasiparticle and excitonic effect. Our results show that these light-induced trapped states can be observed by experiments, as confirmed in other similar systems by the femtosecond transient absorption spectra.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2020

Energetics of Base–Acid Pairs for the Design of High-Temperature Fuel Cell Polymer Electrolytes

The interaction energy of base–acid plays a key role in acid retention of phosphoric acid (PA)-doped polymer electrolytes under fuel cell operating conditions. Here, we investigate the energetics of proton-accepting and hydroxide-donating organic bases using density functional theory calculations. Because of their weak basicity, proton-accepting organic bases such as benzimidazole have relatively low interaction energy with the acid in the absence of water (15.3–28.0 kcal mol –1 ). Energetics of the proton-accepting base–PA complex increases by adding water, indicating that the interactions in the base–acid complex strengthen in the presence of water. On the other hand, hydroxide-donating organic bases, such as tetramethylammonium hydroxide, have high interaction energy with PA (~110 kcal mol –1 ), which remains high in the presence of water. The chemical shifts of 31P NMR support the energetics of the base–acid complexes. Overall, this study further discusses the benefit of incorporating hydroxide-donating organic bases into the polymeric structure over proton-accepting bases as a way to increase acid retention.

25 ENERGY STORAGE↗

DOE OSTI2025

Exploiting a Shortcoming of Coupled-Cluster Theory: The Extent of Non-Hermiticity as a Diagnostic Indicator of Computational Accuracy

The fundamental non-Hermitian nature of the forms of the coupled-cluster (CC) theory widely used in quantum chemistry has usually been viewed as a negative, but the present paper shows how this can be used to an advantage. Specifically, the non-symmetric nature of the reduced one-particle density matrix (in the molecular orbital basis) is advocated as a diagnostic indicator of computational quality. In the limit of the full coupled-cluster theory [which is equivalent to full configuration interaction (FCI)], the electronic wave function and correlation energy are exact within a given one-particle basis set, and the symmetric character of the exact density matrix is recovered. The extent of the density matrix asymmetry is shown to provide a measure of “how difficult the problem is” (like the well-known T 1 diagnostic), but its variation with the level of theory also gives information about “how well this particular method works”, irrespective of the difficulty of the problem at hand. The proposed diagnostic is described and applied to a select group of small molecules, and an example of its overall utility for the practicing quantum chemist is illustrated through its application to the beryllium dimer (Be 2 ). Future application of this idea to excited states, open-shell systems, and symmetry-breaking problems and an extension of the method to the two-particle density are then proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1972

The global energy budget of the thermosphere.

Experimental neutral atmospheric density and temperature profiles can be used to calculate the energy content variations of a given region as a function of time, season and location for which the data are available. Such calculations may then be compared with estimated energy inputs and losses to determine what other mechanisms may be important. In the present paper a model based on both incoherent scatter data from Arecibo, Nancay, and Jicamarca and satellite density measurements is used to derive the global distributions of thermal energy content and losses in the thermosphere. The energy sources and transport mechanisms required for global thermal balance are then discussed.

Swartz, W. E.↗

DOE OSTI2025

Intrinsic Layer-Dependent Surface Energy and Exfoliation Energy of van der Waals Materials

Stacking and twisting 2D van der Waals (vdW) layers have become versatile platforms to tune the electron correlation. These platforms rely on exfoliating vdW materials down to a single vdW layer and a few vdW layers. We calculate the intrinsic layer-dependent surface and exfoliation energies of typical vdW materials such as graphite, h-BN, black P, MX 2 (M = Mo or W; X = S, Se, or Te), MX (M = Ga or In; X = S, Se, or Te), Bi 2 Te 3 , and MnBi 2 Te 4 using density functional theory. For exchange-correlation functionals with explicit vdW interaction, a single vdW layer always has the smallest surface energy, giving a surface energy reduction when compared to that of thicker vdW layers. Furthermore, the magnitude of this surface energy reduction quickly decreases with an increase in the number of atomic layers inside the single vdW layer for different vdW materials. Such atomic-layer dependence in surface energy reduction helps explain the different effectiveness of exfoliation for different vdW materials down to a single vdW layer.

Anode materials↗

NASA NTRS1983

Theoretical study of the freezing of polystyrene sphere suspensions

A theoretical study of melting in aqueous suspensions of polystyrene spheres is presented. The Helmholtz free energies of the liquid and solid phase of the suspensions are calculated as functions of sphere number density and electrolyte concentrations. The results tend to show that the freezing curve of such suspensions is that of a conventional classical liquid with repulsive short-range interactions. The interactions can be treated satisfactorily within a slightly modified Debye-Hueckel approximation. The modifications include size correction and a correction for nonlinear screening. The results are confirmed by analogous calculations for the solid phase, and for the line along which liquid and solid free energies are equal.

Shih, W.-H.↗

DOE OSTI2025

Ba 1−x Sr x FeO 3−δ as an improved oxygen storage material for chemical looping air separation: a computational and experimental study

Chemical looping air separation (CLAS) is a promising technology to generate oxygen-rich gas streams to enable efficient carbon dioxide capture during fossil fuel combustion or gasification. CLAS relies on the capture and release of oxygen from the atmosphere using the redox properties of an oxygen-selective solid oxide carrier. This study investigates the redox characteristics of Ba 1−x Sr x FeO 3−δ (0.0 ≤ x ≤ 0.417, 0.0 ≤ δ ≤ 0.5) using a combination of density functional theory (DFT) calculations and experimental verification using X-ray diffraction, thermogravimetric analysis, and oxygen-temperature-programmed desorption. The DFT computed energies of the Ba 1−x Sr x FeO 3−δ perovskites reveal a composition-dependent transition from hexagonal to cubic phases as the Sr-concentration or oxygen vacancy concentration increases. Oxygen vacancy formation energies of the cubic perovskites are found to be lower than those of their hexagonal counterparts. A low oxygen diffusion barrier of ∼1 eV combined with the thermodynamic preference of Ba 1−x Sr x FeO 3−δ compositions that form in a cubic phase suggests them as promising candidates for oxygen storage applications. The experimental results corroborate this finding by identifying Ba 0.75 Sr 0.25 FeO 3−δ in the cubic phase as an optimal composition offering low-temperature oxygen storage capacities comparable to that of the state-of-the-art Sr 0.75 Ca 0.25 FeO 3−δ perovskite oxygen storage material at 325 °C and 350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Comparative Critical Mass Calculations for NNL and ENDF/B-VIII.0 Zirconium Hydride Thermal Neutron Scattering Laws

Zirconium hydride (ZrH x ) is a moderator material for TRIGA reactors and historical space reactor systems, such as SNAP-10A. Thermal neutron scattering laws (TSL) for two phases of this material, δ and ε, have been previously evaluated by Naval Nuclear Laboratory (NNL) and submitted to the National Nuclear Data Center (NNDC) for inclusion in the US national ENDF/B-VIII.1 nuclear data library. In contrast to the current ENDF/B-VIII.0 TSL evaluations, which consider only a single phase, the new evaluations are derived from separate ab initio calculations for both phases and include coherent elastic effects of the zirconium sublattice. To estimate the impact of these changes to the TSL evaluation of this material, comparative critical mass calculations were performed with MC21 for homogenous mixtures of high- enriched uranium (HEU) and ZrH x in bare and water reflected sphere configurations. These calculations yield an impact on the estimated critical mass as a function of 235 U loading density with maximum differences as large as 1% - 5% for over-moderated thermal spectrum systems. Consequently, the NNL TSL evaluations are anticipated to have a small impact on criticality calculations of thermal reactor systems regardless of the material phase. Nevertheless, characteristic differences exist in the predicted thermal spectra as function of energy for the two sets of TSL evaluations, which are attributed to difference in the underlying phonon density of states of hydrogen bound in ZrH x .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2022

Comparative critical mass calculations for NNL and ENDF/B-VIII.0 - Zirconium hydride thermal neutron scattering laws

Zirconium hydride (ZrH{sub x}) is a moderator material for TRIGA reactors and historical space reactor systems, such as SNAP-10A. Thermal neutron scattering laws (TSL) for two phases of this material, δ and ε, have been previously evaluated by Naval Nuclear Laboratory (NNL) and submitted to the National Nuclear Data Center (NNDC) for inclusion in the US national ENDF/B-VIII.1 nuclear data library. In contrast to the current ENDF/B-VIII.0 TSL evaluations, which consider only a single phase, the new evaluations are derived from separate ab initio calculations for both phases and include coherent elastic effects of the zirconium sublattice. To estimate the impact of these changes to the TSL evaluation of this material, comparative critical mass calculations were performed with MC21 for homogenous mixtures of high-enriched uranium (HEU) and ZrH{sub x} in bare and water reflected sphere configurations. These calculations yield an impact on the estimated critical mass as a function of {sup 235}U loading density with maximum differences as large as 1% - 5% for over-moderated thermal spectrum systems. Consequently, the NNL TSL evaluations are anticipated to have a small impact on criticality calculations of thermal reactor systems regardless of the material phase. Nevertheless, characteristic differences exist in the predicted thermal spectra as function of energy for the two sets of TSL evaluations, which are attributed to difference in the underlying phonon density of states of hydrogen bound in ZrH{sub x}. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2020

Kβ X-ray Emission Spectroscopy as a Probe of Cu(I) Sites: Application to the Cu(I) Site in Preprocessed Galactose Oxidase

Cu(I) active sites in metalloproteins are involved in O 2 activation, but their O 2 reactivity is difficult to study due to the Cu(I) d 10 closed shell which precludes the use of conventional spectroscopic methods. Kβ X-ray emission spectroscopy (XES) is a promising technique for investigating Cu(I) sites as it detects photons emitted by electronic transitions from occupied orbitals. Here, we demonstrate the utility of Kβ XES in probing Cu(I) sites in model complexes and a metalloprotein. Using Cu(I)Cl, emission features from double-ionization (DI) states are identified using varying incident X-ray photon energies, and a reasonable method to correct the data to remove DI contributions is presented. Kβ XES spectra of Cu(I) model complexes, having biologically relevant N/S ligands and different coordination numbers, are compared and analyzed, with the aid of density functional theory (DFT) calculations, to evaluate the sensitivity of the spectral features to the ligand environment. While the low-energy Kβ 2,5 emission feature reflects the ionization energy of ligand np valence orbitals, the high-energy Kβ 2,5 emission feature corresponds to transitions from molecular orbitals (MOs) having mainly Cu 3d character with the intensities determined by ligand-mediated d–p mixing. A Kβ XES spectrum of the Cu(I) site in preprocessed galactose oxidase (GO pre ) supports the 1Tyr/2His structural model that was determined by our previous X-ray absorption spectroscopy and DFT study. Finally, the high-energy Kβ 2,5 emission feature in the Cu(I)-GO pre data has information about the MO containing mostly Cu 3d x 2 –y 2 character that is the frontier molecular orbital (FMO) for O 2 activation, which shows the potential of Kβ XES in probing the Cu(I) FMO associated with small-molecule activation in metalloproteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Ab Initio Structures and Energetics of Hydrated Flat and Terrace-Step Surfaces of Forsterite (Mg 2 SiO 4 )

Forsterite (Mg 2 SiO 4 ), a model divalent metal silicate mineral, has been extensively studied in the context of mineral carbonation. Although dissolution is a key step in this process, the mechanisms by which forsterite dissolves under high CO 2 conditions remain poorly understood. Atomistic simulations could aid in exploring these mechanisms, but it is essential first to understand the structures and energetics of the relevant forsterite surfaces. We present an ab initio study of the structure and surface energy at 0 K of the flat $(010), (110), (001), (111), (021), (101)$ and $(120)$ faces of forsterite using the density functional PBE Hamiltonian and a plane-wave basis set. Dry surfaces became stabilized upon hydration through the formation of bonds between surface Mg and O from water, as well as by the formation of hydrogen bonds. According to surface energy values, the stability order of the hydrated forsterite faces was found to be $(120) < (101) < (021) < (111) < (001) < (110) < (010)$. We also investigated the energetics of the terrace-step $(0\bar{41})$ surface as a model site for forsterite dissolution. Among all the facets, the $(0\bar{41})$ surface is the least stable termination in water. Hydration of Mg atoms on the $(0\bar{41})$ surface increases their susceptibility to dissolution. The presence of a step and its hydration destabilizes the terraces, making step retreat more likely than a dissolution front advancing along the [010] direction. This research will support future simulations to investigate forsterite dissolution in water under CO 2 -rich conditions.

PBE Hamiltonian↗

NASA NTRSDate not supplied

SelenITA: A dual-spacecraft lunar CubeSat mission to characterize the near-surface electromagnetic plasma environment

SelenITA is an international interdisciplinary mission consisting of two CubeSats that will provide the first multi-point measurement in a sustained low lunar orbit. This mission will advance the understanding of spatiotemporal differentiation of the electromagnetic space environment at the Moon in support of Artemis crew and the geosciences. The mission science objectives are to: (1) further constrain the origins of crustal magnetic fields and their applications; (2) determine the nature of plasma interactions with crustal magnetic fields; (3) characterize plasma waves and turbulence at the Moon; (4) characterize the lunar surface potential in all plasma environments; (5) constrain the composition, thermal state, and structure of the lunar upper mantle and crust; (6) characterize the ionizing radiation in lunar orbit; (7) determine the density of the dust exosphere as a function of latitude, longitude, and altitude, including the lunar polar space environment. The measurement requirements include: 3-component vector magnetic field, plasma distribution (flux, energy, density, temperature), energetic particles (protons, electrons, gamma rays), and dust. SelenITA builds on a rich history of electromagnetic plasma observations of the near lunar surface and space environment, and it answers high level science questions with state of the art instruments in a small package. PLAIN LANGUAGE ABSTRACT – SelenITA comes from the greek word for Moon, selene, with the addition of “ITA” as a reference to the Brazilian teammate, Instituto Tecnológico de Aeronáutica. In addition, in Portuguese "ita" is a prefix similar to "ite" in English, used in naming minerals, so Selenita could be seen as a lunar gemstone. In Spanish, “ita” is a diminutive suffix for “little” which is appropriate for this CubeSat mission which consists of twin 12U CubeSats in low lunar orbit. The primary science goal of the mission is to distinguish time varying features within the electromagnetic plasma environment near the surface of the Moon. The science objectives include investigating the origins of crustal magnetic fields, plasma interactions with these fields, plasma waves, surface potential, and interior properties. This mission is also interested in the radiation environment at the Moon and the amount of dust at the lunar poles. This is important because it helps us understand how future astronauts will live and work on the lunar surface and identify hazards.

space weather↗

NASA NTRSDate not supplied

SelenITA: A Dual-Spacecraft Lunar Cubesat Mission to Characterize the Near-Surface Electromagnetic Plasma Environment

SelenITA is an international interdisciplinary mission consisting of two CubeSats that will provide the first multi-point measurement in a sustained low lunar orbit. This mission will advance the understanding of spatiotemporal differentiation of the electromagnetic space environment at the Moon in support of Artemis crew and the geosciences. The mission science objectives are to: (1) further constrain the origins of crustal magnetic fields and their applications; (2) determine the nature of plasma interactions with crustal magnetic fields; (3) characterize plasma waves and turbulence at the Moon; (4) characterize the lunar surface potential in all plasma environments; (5) constrain the composition, thermal state, and structure of the lunar upper mantle and crust; (6) characterize the ionizing radiation in lunar orbit; (7) determine the density of the dust exosphere as a function of latitude, longitude, and altitude, including the lunar polar space environment. The measurement requirements include: 3-component vector magnetic field, plasma distribution (flux, energy, density, temperature), energetic particles (protons, electrons, gamma rays), and dust. SelenITA builds on a rich history of electromagnetic plasma observations of the near lunar surface and space environment, and it answers high level science questions with state of the art instruments in a small package.

space weather↗

NASA NTRSDate not supplied

SelenITA: A Dual-Spacecraft Lunar CubeSat Mission to Characterize the Near-Surface Electromagnetic Plasma Environment

SelenITA is an international interdisciplinary mission consisting of two CubeSats that will provide the first multi-point measurement in a sustained low lunar orbit. This mission will advance the understanding of spatiotemporal differentiation of the electromagnetic space environment at the Moon in support of Artemis crew and the geosciences. The mission science objectives are to: (1) further constrain the origins of crustal magnetic fields and their applications; (2) determine the nature of plasma interactions with crustal magnetic fields; (3) characterize plasma waves and turbulence at the Moon; (4) characterize the lunar surface potential in all plasma environments; (5) constrain the composition, thermal state, and structure of the lunar upper mantle and crust; (6) characterize the ionizing radiation in lunar orbit; (7) determine the density of the dust exosphere as a function of latitude, longitude, and altitude, including the lunar polar space environment. The measurement requirements include: 3-component vector magnetic field, plasma distribution (flux, energy, density, temperature), energetic particles (protons, electrons, gamma rays), and dust. SelenITA builds on a rich history of electromagnetic plasma observations of the near lunar surface and space environment, and it answers high level science questions with state of the art instruments in a small package. PLAIN LANGUAGE ABSTRACT – SelenITA comes from the greek word for Moon, selene, with the addition of “ITA” as a reference to the Brazilian teammate, Instituto Tecnológico de Aeronáutica. In addition, in Portuguese "ita" is a prefix similar to "ite" in English, used in naming minerals, so Selenita could be seen as a lunar gemstone. In Spanish, “ita” is a diminutive suffix for “little” which is appropriate for this CubeSat mission which consists of twin 12U CubeSats in low lunar orbit. The primary science goal of the mission is to distinguish time varying features within the electromagnetic plasma environment near the surface of the Moon. The science objectives include investigating the origins of crustal magnetic fields, plasma interactions with these fields, plasma waves, surface potential, and interior properties. This mission is also interested in the radiation environment at the Moon and the amount of dust at the lunar poles. This is important because it helps us understand how future astronauts will live and work on the lunar surface and identify hazards.

space weather↗